Endless tubular polyimide film

ABSTRACT

The present invention provides a method for producing a high-quality nonconductive or semi-conductive seamless (jointless) tubular polyimide film in a simple, efficient, and economical manner, and the like. More specifically, the invention relates to an electrically non-conductive or electrically semi-conductive seamless tubular polyimide film comprising polyimide having at least two aromatic tetracarboxylic acid derivatives comprising 15 to 55 mol % of asymmetric aromatic tetracarboxylic acid component and 85 to 45 mol % of symmetric aromatic tetracarboxylic acid component and at least one aromatic diamine component, in which, as required, a specific amount of carbon black is dispersed, and relates to a method for producing the same.

TECHNICAL FIELD

The present invention relates to an improved non-conductive orsemi-conductive seamless tubular polyimide film and a production methodtherefor. The semi-conductive seamless tubular polyimide film is used,for example, as an intermediate transfer belt and the like in anelectrophotographic system for use in a color printer, color copier,etc.

BACKGROUND OF THE INVENTION

It is well known that a non-conductive tubular polyimide film isgenerally processed into a belt form to be used, for example, as a beltfor conveying heated materials and a fixing belt for use in anelectrophotographic system.

Moreover, a semi-conductive tubular polyimide film comprising conductivecarbon black mixed and dispersed in a non-conductive tubular polyimidefilm is used as an intermediate transfer belt for use in, for example,copiers, printers, facsimiles, and presses.

It is known that such non-conductive and semi-conductive tubularpolyimide films are prepared by forming a predetermined film-formationstarting material into a flat film, and jointing both ends of the flatfilm to form a tubular shape; or by forming a predeterminedfilm-formation starting material into a seamless tubular film bycentrifugal casting in a single step. Japanese Unexamined PatentPublication No. 2000-263568 filed by the applicant of the presentapplication discloses performing centrifugal casting under substantiallyno centrifugal force to form a tubular shape.

In general, a solution of polyamide acid (or polyamic acid) withhigh-molecular-weight (a number average molecular weight: usually about10000 to about 30000), i.e., a polymer precursor of a polyimide, is usedas a film-formation starting material for such tubular polyimide films.

More specifically, the polyamic acid solution is produced bypolycondensation of aromatic tetracarboxylic dianhydride and anequimolar amount of aromatic diamine in an organic polar solvent at lowtemperatures at which no imidization occurs. Examples of the aromatictetracarboxylic dianhydride include 1,2,4,5-benzene tetracarboxylicdianhydride, 3,3′,4,4′-biphenyl tetracarboxylic dianhydride,3,3′,4,4′-benzophenone tetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, etc., in which the anhydride groups arepoint-symmetrically arranged. Examples of aromatic diamines includep-phenylenediamine, 4,4′-diaminodiphenylether,4,4′-diaminodiphenylmethane, etc.

The method for producing a polyimide film ordinarily comprises threesteps: preparing a polyamic acid solution as a film-formation startingmaterial; forming this into a polyamic acid film; and imidizing theformed film.

However, a polyamic acid solution obtained by the preparation stepsdescribed above is disadvantageous in that a partial gel is likely to begradually formed during storage due to the pot life thereof. Suchpartial formation of gel is likely to occur at high temperatures, but itproceeds with time even at low temperatures. Thus, even when the gelformation is negligible, it is a matter of course that the physicalproperties of the finished polyimide film prepared from such a solutionare adversely affected and, in addition, the flatness of the film isdiminished. In particular, the addition of conductive carbon black tothe polyimide film leads to an increase in the variation of electricalresistance.

Moreover, since the solubility of polyamic acid resins in an organicpolar solvent is limited, it is difficult to form a solution containinga high concentration thereof (at most 25% by weight in terms of thenonvolatile matter content in a solution).

In some cases, the addition of carbon black to the polyamic acidsolution sharply increases viscosity, which makes it difficult to grindthe carbon black by the impulsive force generated between the balls in adispersing apparatus such as a ball mill. In order to uniformlydispersing carbon black in a polyamic acid solution, pulverizability ofcarbon black with a disperser and the interfacial phenomenon referred toas “wetting” of carbon black disintegrated by a solvent are required.Therefore, a large amount of organic polar solvent is added to uniformlydisperse the carbon black. As a result, however, the nonvolatile mattercontent in the obtained masterbatch solution containing a highconcentration of carbon black is as low as 16% by weight or less.

Furthermore, a solution containing a low concentration of polyamic acidhas drawbacks in that a thicker film is difficult to form in a singlestep, and in that since a larger amount of solvent is required, theperiod of time for removing the large amount of solvent by evaporationis prolonged.

Because the three steps described above are included in the polyimidefilm preparation method, the entire process requires considerable timeand cost. Thus, there is room for improving efficiency and cost.

Japanese Unexamined Patent Publication No. 10-182820 discloses afilm-formation method using a polyimide precursor composition comprisingas a main component a monomer having a mixture of aromatictetracarboxylic acid component comprising as a main component asymmetricaromatic tetracarboxylic acid and/or ester thereof (specifically 60 mol% or more of 2,3,3′4′-biphenyl tetracarboxylic acid and/or esterthereof) and an approximately equimolar amount of an aromatic diaminecomponent. Moreover, Japanese Unexamined Patent Publication No.10-182820 discloses a method for forming a polyimide film by applying apolyimide precursor composition to a glass plate by pouring the samethereon and then heating the result (raising the temperature stepwise inthe range of 80° C. to 350° C.), and also discloses using the polyimidefilm as an electrically conductive paste by the addition of silverpowder, copper powder, carbon black, etc.

However, a semi-conductive polyimide film obtained by theabove-mentioned film formation method has further room for improvementin its properties, such as electrical resistance, etc., when it is usedas an intermediate transfer belt or the like in an electrophotographicsystem for use in color printers, color copiers, etc., which arerequiring high accuracy in recent years.

DISCLOSURE OF THE INVENTION

The present invention aims, considering the above-described problems ofthe prior art, to provide a high-quality electrically non-conductive orelectrically semi-conductive seamless (jointless) tubular polyimide filmand a method for producing the same in a simple, efficient andeconomical manner.

The inventors of the present invention carried out intensive research soas to solve the above problems and finally found that a high-qualityseamless tubular polyimide film can be obtained by rotationally moldinga mixed solution substantially in a monomeric state comprising a mixtureof an aromatic tetracarboxylic acid component comprising a specificamount of asymmetric aromatic tetracarboxylic acid and/or ester thereofand a specific amount of symmetric aromatic tetracarboxylic acid and/orester thereof and an approximately equimolar amount of an aromaticdiamine component, to form a tubular shape, and imidizing the tubularmaterial by heating.

More specifically, the present invention provides the followingnon-conductive or semi-conductive seamless tubular polyimide films.

-   Item 1. A seamless tubular polyimide film, comprising polyimide    having at least two aromatic tetracarboxylic acid components having    a mixture of 15 to 55 mol % of asymmetric aromatic tetracarboxylic    acid component and 85 to 45 mol % of symmetric aromatic    tetracarboxylic acid component and at least one aromatic diamine    component, the seamless tubular polyimide film having a yield stress    (σ_(Y)) of at least 120 MPa and having a tensile strength to yield    stress ratio (σ_(cr)/σ_(Y)) of at least 1.10.-   Item 2. A semi-conductive seamless tubular polyimide film, wherein    carbon black is dispersed in polyimide having at least two aromatic    tetracarboxylic acid components having a mixture of 15 to 55 mol %    of asymmetric aromatic tetracarboxylic acid component and 85 to 45    mol % of symmetric aromatic tetracarboxylic acid component and at    least one aromatic diamine component, the semi-conductive seamless    tubular polyimide film having a surface resistivity of 10³ to 10¹⁵    Ω/sq.-   Item 3. A semi-conductive seamless tubular polyimide film according    to Item 2, wherein    -   a log standard deviation of surface resistivity is 0.2 or        smaller,    -   a log standard deviation of volume resistivity is 0.2 or        smaller, and    -   a difference between a log surface resistivity and a log volume        resistivity is 0.4 or smaller.

The invention has the above-described properties, and furtherencompasses the following first, second, third and fourth embodiments.

A. FIRST EMBODIMENT

The inventors of the present invention found that a high-qualityelectrically semi-conductive seamless tubular polyimide film can beobtained by rotational molding of an electrically semiconductivepolyimide precursor composition in which a specific amount of carbonblack is dispersed in a mixed solution substantially in a monomericstate having a mixture of an aromatic tetracarboxylic acid componentcomprising a specific amount of asymmetric aromatic tetracarboxylic acidand/or ester thereof and a specific amount of symmetric aromatictetracarboxylic acid and/or ester thereof and an approximately equimolaramount of an aromatic diamine component, to form a tubular shape, andimidizing the tubular material by heating.

The inventors have conducted further study based on this finding andaccomplished the following invention (hereinafter referred to as the“first embodiment”).

The first embodiment provides the following electrically non-conductiveor electrically semi-conductive seamless tubular polyimide films andproduction methods therefor.

-   Item 4. A method for producing a seamless tubular polyimide film,    comprising:    -   rotationally molding a mixed solution substantially in a        monomeric state having a mixture of an aromatic tetracarboxylic        acid component comprising 15 to 55 mol % of asymmetric aromatic        tetracarboxylic acid and/or ester thereof and 85 to 45 mol % of        symmetric aromatic tetracarboxylic acid and/or ester thereof and        an approximately equimolar amount of an aromatic diamine        component, to form a tubular shape, and    -   imidizing the tubular material by heating.-   Item 5. A method for producing a semi-conductive seamless tubular    polyimide film, comprising:    -   mixing an aromatic tetracarboxylic acid component comprising 15        to 55 mol % of asymmetric aromatic tetracarboxylic acid and/or        ester thereof and 85 to 45 mol % of symmetric aromatic        tetracarboxylic acid and/or ester thereof and an approximately        equimolar amount of an aromatic diamine component, to form mixed        solution substantially in a monomeric state,    -   dispersing 1 to 35 parts by weight of carbon black in the mixed        solution, per 100 parts by weight of a total amount of the        aromatic tetracarboxylic acid component and the aromatic diamine        component, to form a semi-conductive monomer mixed solution,    -   rotationally molding the semiconductive monomer mixed solution        to form a tubular shape; and    -   imidizing the tubular material by heating.-   Item 6. A semi-conductive seamless tubular polyimide film for use in    an intermediate transfer belt in an electrophotographic system    produced by a production method of Item 5.

B. SECOND EMBODIMENT

The inventors of the present invention carried out intensive research tosolve the above problems and finally found that an electricallysemi-conductive seamless tubular polyimide film with uniform electricalresistivity can be obtained by heating an aromatic tetracarboxylic acidderivative and an aromatic diamine to substantially undergo partialpolycondensation, thereby yielding a mixed solution comprising anaromatic amic acid oligomer (number average molecular weight: about 1000to about 7000); mixing electrically conductive carbon black in the mixedsolution; rotationally molding the mixture; and imidizing the resultant.The inventors have conducted further study based on this finding andaccomplished the following invention (hereinafter referred to as the“second embodiment”).

More specifically, the second embodiment provides the followingelectrically semi-conductive aromatic amic acid compositions andproduction methods therefor, and electrically semiconductive seamlesstubular polyimide films and production methods therefor.

-   Item 7. A semi-conductive aromatic amic acid composition comprising:    -   an aromatic amic acid oligomer obtained by polycondensation of        at least two aromatic tetracarboxylic acid derivatives and an        approximately equimolar amount of at least one aromatic diamine;    -   carbon black; and    -   an organic polar solvent.-   Item 8. A semi-conductive aromatic amic acid composition according    to Item 7, wherein the aromatic amic acid oligomer is obtained by    polycondensation of at least two aromatic tetracarboxylic    dianhydrides and an approximately equimolar amount of said at least    one aromatic diamine in an organic polar solvent at about 80° C. or    lower.-   Item 9. A semi-conductive aromatic amic acid composition according    to Item 8, wherein said at least two aromatic tetracarboxylic    dianhydrides are 15 to 55 mol % of asymmetric aromatic    tetracarboxylic dianhydride and 85 to 45 mol % of symmetric aromatic    tetracarboxylic dianhydride.-   Item 10. A semi-conductive aromatic amic acid composition according    to Item 7, wherein the aromatic amic acid oligomer is obtained by    polycondensation of at least two aromatic tetracarboxylic acid    diesters and an approximately equimolar amount of said at least one    aromatic diamine in an organic polar solvent at about 90 to about    120° C.-   Item 11. A semi-conductive aromatic amic acid composition according    to Item 10, wherein said at least two aromatic tetracarboxylic acid    diesters are 15 to 55 mol % of asymmetric aromatic tetracarboxylic    acid diester and 85 to 45 mol % of symmetric aromatic    tetracarboxylic acid diester.-   Item 12. A semi-conductive aromatic amic acid composition according    to Item 7, wherein a number average molecular weight of the aromatic    amic acid oligomer is about 1000 to about 7000.-   Item 13. A semi-conductive aromatic amic acid composition according    to Item 7, wherein carbon black is present in an amount of about 3    to about 30 parts by weight per 100 parts by weight of a total    amount of aromatic tetracarboxylic acid component and organic    diamine.-   Item 14. A method for producing a semi-conductive seamless tubular    polyimide film, comprising:    -   rotationally molding a semi-conductive aromatic amic acid        composition according to Item 7; followed by heating.-   Item 15. A semi-conductive seamless tubular polyimide film for use    in an intermediate transfer belt in an electrophotographic system    produced by a production method according to Item 14.-   Item 16. A method for producing a semi-conductive aromatic amic acid    composition comprising:    -   subjecting at least two aromatic tetracarboxylic acid        derivatives and an approximately equimolar amount of at least        one aromatic diamine to partial condensation polymerization in        an organic polar solvent, thereby yielding an aromatic amic acid        oligomer solution; and    -   uniformly mixing electrically conductive carbon black powder        with the oligomer solution.

C. THIRD EMBODIMENT

The inventors of the present invention carried out intensive research tosolve the above problems and finally found that excellent dispersionstability of carbon black is achieved in a mixed solution obtained bymixing a high-molecular-weight polyimide precursor solution or ahigh-molecular-weight polyamideimide solution in a nylon salt monomersolution obtained by dissolving at least two aromatic tetracarboxylicacid diesters and an approximately equimolar amount of at least onearomatic diamine in an organic polar solvent. Moreover, the inventorsfound that a semi-conductive seamless tubular polyimide film havinguniform electrical resistivity can be obtained by rotationally moldingan electrically semi-conductive polyimide-based precursor composition,obtained by uniformly mixing the above mixed solution and carbon black,and imidizing the resultant. The present invention is accomplished byfurther applying these findings (hereinafter referred to as the “thirdembodiment”).

More specifically, the third embodiment provides the followingelectrically semi-conductive polyimide-based precursor compositions andproduction methods therefor, and electrically semi-conductive seamlesstubular polyimide-based films and production methods therefor.

-   Item 17. A semi-conductive polyimide-based precursor composition,    wherein carbon black is uniformly dispersed in a mixed solution    prepared by mixing a high-molecular-weight polyimide precursor    solution or high-molecular-weight polyamideimide solution in a nylon    salt monomer solution in which at least two aromatic tetracarboxylic    acid diesters and an approximately equimolar amount of at least one    aromatic diamine are dissolved in an organic polar solvent.-   Item 18. A semi-conductive polyimide-based precursor composition    according to Item 17, wherein said at least two aromatic    tetracarboxylic acid diesters are 10 to 55 mol % of asymmetric    aromatic tetracarboxylic acid diester and 90 to 45 mol % of    symmetric aromatic tetracarboxylic acid diester.-   Item 19. A semi-conductive polyimide-based precursor composition    according to Item 17, wherein said at least two aromatic    tetracarboxylic acid diesters are 10 to 55 mol % of asymmetric    2,3,3′,4′-biphenyl tetracarboxylic acid diester and 90 to 45 mol %    of symmetric 3,3′,4,4′-biphenyl tetracarboxylic acid diester.-   Item 20. A semi-conductive polyimide-based precursor composition    according to Item 17, wherein the high-molecular-weight polyimide    precursor solution is a polyamic acid solution whose number average    molecular weight is 10000 or larger and the high-molecular-weight    polyamideimide solution is a polyamideimide solution whose number    average molecular weight is 10000 or larger.-   Item 21. A semi-conductive polyimide-based precursor composition    according to Item 20, wherein the polyamic acid solution whose    number average molecular weight is 10000 or larger is produced by    reaction of diaminodiphenyl ether and an approximately equimolar    amount of biphenyltetracarboxylic dianhydride in an organic polar    solvent.-   Item 22. A semi-conductive polyimide-based precursor composition    according to Item 20, wherein the polyamideimide solution whose    number average molecular weight is 10000 or larger is produced by    reaction of acid anhydride comprising trimellitic acid anhydride and    benzophenone tetracarboxylic dianhydride and an approximately    equimolar amount of aromatic isocyanate in an organic polar solvent.-   Item 23. A method for producing a semi-conductive seamless tubular    polyimide film, comprising:    -   rotationally molding a semi-conductive polyimide-based precursor        composition according to Item 17, to form a tubular shape; and    -   imidizing the tubular material by heating.-   Item 24. A semi-conductive seamless tubular polyimide-based film for    use in an intermediate transfer belt in an electrophotographic    system produced by a production method according to Item 23, whose    surface resistivity is 10⁷ to 10⁴ Ω/sq.-   Item 25. A method for producing a semi-conductive polyimide-based    precursor composition, comprising:    -   mixing a high-molecular-weight polyimide precursor solution or        high-molecular-weight polyamideimide solution in a nylon salt        monomer solution in which at least two aromatic tetracarboxylic        acid diesters and an approximately equimolar amount of at least        one aromatic diamine are dissolved in an organic polar solvent        to prepare a mixed solution, and    -   uniformly dispersing carbon black in the mixed solution.

D. FOURTH EMBODIMENT

The inventors of the present invention carried out intensive research tosolve the above problems and finally found that a high-concentrationelectrically semi-conductive polyimide precursor composition withexcellent dispersibility of carbon black can be obtained by uniformlydispersing carbon black in an organic polar solvent to give a carbonblack dispersion and dissolving aromatic tetracarboxylic acid diesterand an approximately equimolar amount of aromatic diamine in the carbonblack dispersion. The inventors also found that an electricallysemi-conductive seamless tubular polyimide film with uniform electricalresistivity can be obtained by rotationally molding a high-concentrationelectrically semi-conductive polyimide precursor composition, followedby imidizing. The present invention is accomplished by further applyingthese findings (hereinafter referred to as “fourth embodiment”).

More specifically, the fourth embodiment provides the followinghigh-concentration electrically semi-conductive polyimide precursorcompositions and production methods therefor, and electricallysemi-conductive seamless tubular polyimide films using the same andproduction methods therefor.

-   Item 26. A method for producing a high-concentration semi-conductive    polyimide precursor composition, comprising:    -   uniformly dispersing carbon black in an organic polar solvent to        give a carbon black dispersion and    -   dissolving aromatic tetracarboxylic acid diester and an        approximately equimolar amount of aromatic diamine in the carbon        black dispersion.-   Item 27. A method for producing a high-concentration semi-conductive    polyimide precursor composition according to Item 26, wherein the    aromatic tetracarboxylic acid diester is a mixture of 10 to 55 mol %    of asymmetric aromatic tetracarboxylic acid diester and 90 to 45 mol    % of symmetric aromatic tetracarboxylic acid diester.-   Item 28. A method for producing a high-concentration semi-conductive    polyimide precursor composition according to Item 26, wherein the    aromatic tetracarboxylic acid diester is a mixture of 10 to 55 mol %    of asymmetric 2,3,3′,4′-biphenyl tetracarboxylic acid diester and 90    to 45 mol % of symmetric 3,3′,4,4′-biphenyl tetracarboxylic acid    diester.-   Item 29. A method for producing a high-concentration semi-conductive    polyimide precursor composition according to Item 26, wherein carbon    black is present in an amount of 5 to 35 parts by weight per 100    parts by weight of a total amount of the aromatic tetracarboxylic    acid and the aromatic diamine.-   Item 30. A high-concentration semi-conductive polyimide precursor    composition produced by a production method of Item 26.-   Item 31. A method for producing a semi-conductive seamless tubular    polyimide film, comprising:    -   rotationally molding a high-concentration semi-conductive        polyimide precursor composition according to Item 30, to form a        tubular shape; and    -   imidizing the tubular material by heating.-   Item 32. A semi-conductive seamless tubular polyimide film for use    in an intermediate transfer belt in an electrophotographic system    produced by a method according to Item 31, whose surface resistivity    is 10⁷ to 10¹⁴ Ω/sq.

DETAILED DESCRIPTION OF INVENTION

Hereinafter, the present invention is described in detail in “A. FirstEmbodiment” “B. Second Embodiment” “C. Third Embodiment” and “D. FourthEmbodiment”.

A. FIRST EMBODIMENT

A-1. Seamless Tubular Polyimide Film

The seamless tubular polyimide film (hereinafter sometimes referred toas “tubular PI film”) of the present invention is obtained by using aspecific aromatic tetracarboxylic acid component and a specific aromaticdiamine component as starting materials. Specifically, the electricallynon-conductive tubular PI film of the invention is obtained by using aspecific aromatic tetracarboxylic acid component and a specific aromaticdiamine component as starting materials, and the electricallysemi-conductive tubular PI film of the invention is obtained by using,in addition to the above starting materials, a predetermined amount ofcarbon black (hereinafter sometimes referred to as “CB”) so as to impartconductivity.

Aromatic Tetracarboxylic Acid Component

A mixture of an asymmetric aromatic tetracarboxylic acid component (atleast one member selected from the group consisting of asymmetricaromatic tetracarboxylic acids and esters thereof) and a symmetricaromatic tetracarboxylic acid component (at least one member selectedfrom symmetric aromatic tetracarboxylic acids and esters thereof) isused as the aromatic tetracarboxylic acid component starting material.

Examples of asymmetric aromatic tetracarboxylic acids include:

compounds in which four carboxyl groups are boundnon-point-symmetrically to a monocyclic or polycyclic aromatic ringsystem (e.g., benzene nucleus, naphthalene nucleus, biphenyl nucleus,and anthracene nucleus); and

compounds in which four carboxyl groups are boundnon-point-symmetrically to two monocyclic aromatic rings (e.g., benzenenuclei) linked by a group such as —CO—, —CH₂— or —SO₂—, or by a singlebond.

Specific examples of asymmetric aromatic tetracarboxylic acids include1,2,3,4-benzenetetracarboxylic acid, 1,2,6,7-naphthalenetetracarboxylicacid, 2,3,3′,4′-biphenyltetracarboxylic acid,2,3,3′,4′-benzophenonetetracarboxylic acid, 2,3,3′,4′-diphenyl ethertetracarboxylic acid, 2,3,3′,4′-diphenylmethanetetracarboxylic acid, and2,3,3′,4′-diphenylsulfonetetracarboxylic acid.

Examples of asymmetric aromatic tetracarboxylic acid esters for use inthe present invention include diesters of such asymmetric aromatictetracarboxylic acids (i.e., half esterified). Specific examples thereofinclude compounds in which two of the four carboxyl groups of theasymmetric aromatic tetracarboxylic acid are esterified with one of eachpair of adjacent carboxyl groups on an aromatic ring being esterified.

Examples of the two esters of such asymmetric aromatic tetracarboxylicacid diesters include di(lower alkyl)esters, and preferably di(C₁₋₃alkyl)esters, such as dimethyl esters, diethyl esters, and dipropylesters (particularly, dimethyl esters).

Among such asymmetric aromatic tetracarboxylic acid diesters,2,3,3′,4′-biphenyltetracarboxylic acid dimethyl esters and2,3,3′,4′-biphenyltetracarboxylic acid diethyl esters are preferable,with 2,3,3′,4′-biphenyltetracarboxylic acid dimethyl esters beingparticularly preferable.

Asymmetric aromatic tetracarboxylic acid diesters as above arecommercially available, and can also be produced by known methods. Theycan be easily produced, for example, by a known method of reacting thecorresponding asymmetric aromatic tetracarboxylic dianhydride with thecorresponding alcohol (e.g., lower alcohol, preferably C₁₋₃ alcohol) ata molar ratio of 1:2. By such a method, the acid anhydride, which is astarting material, reacts with the alcohol and thereby undergoes ringopening, providing a diester (half esterified) having an ester group anda carboxyl group on respective adjacent carbons on an aromatic ring.

Examples of symmetric aromatic tetracarboxylic acids include:

compounds in which four carboxyl groups are bound point-symmetrically toa monocyclic or polycyclic aromatic ring system (e.g., benzene nucleus,naphthalene nucleus, biphenyl nucleus, and anthracene nucleus); and

compounds in which four carboxyl groups are bound point-symmetrically totwo monocyclic aromatic rings (e.g., benzene nuclei) linked by a groupsuch as —CO—, —O—, —CH₂— or —SO₂—, or by a single bond.

Specific examples of symmetric aromatic tetracarboxylic acids include1,2,4,5-benzenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylicacid, 3,3′,4,4′-biphenyltetracarboxylic acid, 3,3′,4,4′-benzophenonetetracarboxylic acid, 3,3′,4,4′-diphenyl ether tetracarboxylic acid,3,3′,4,4′-diphenylmethanetetracarboxylic acid, and3,3′,4,4′-diphenylsulfonetetracarboxylic acid.

Examples of symmetric aromatic tetracarboxylic acid esters for use inthe present invention include diesters of such symmetric aromatictetracarboxylic acids (i.e., half esterified). Specific examples thereofinclude compounds in which two of the four carboxyl groups of thesymmetric aromatic tetracarboxylic acid are esterified with one of eachpair of adjacent carboxyl groups on an aromatic ring being esterified.

Examples of the two esters of such symmetric aromatic tetracarboxylicacid diesters include di(lower alkyl)esters, and preferably C₁₋₃ alkylesters, such as dimethyl esters, diethyl esters, and dipropyl esters(particularly, dimethyl esters).

Among such symmetric aromatic tetracarboxylic acid diesters,3,3′,4,4′-biphenyltetracarboxylic acid dimethyl esters,3,3′,4,4′-biphenyltetracarboxylic acid diethyl esters, and2,3,5,6-benzenetetracarboxylic acid dimethyl esters are preferable, with3,3′,4,4′-biphenyltetracarboxylic acid dimethyl esters beingparticularly preferable.

Symmetric aromatic tetracarboxylic acid diesters as above arecommercially available, and can also be produced by known methods. Theycan be easily produced, for example, by reacting the correspondingsymmetric aromatic tetracarboxylic dianhydride with the correspondingalcohol (e.g., lower alcohol, preferably C₁₋₃ alcohol) at a molar ratioof 1:2. By such a method, the acid anhydride, which is a startingmaterial, reacts with the alcohol and thereby undergoes ring opening,providing a diester (half esterified) having an ester group and acarboxyl group on respective adjacent carbons on an aromatic ring.

The mixing ratio for asymmetric and symmetric aromatic tetracarboxylicacids and/or esters thereof is specified such that the proportion ofasymmetric aromatic tetracarboxylic acid(s) and/or ester(s) thereof isabout 15 to about 55 mol % (and preferably about 20 to about 50 mol %)and the proportion of symmetric aromatic tetracarboxylic acid(s) orester(s) thereof is about 85 to about 45 mol % (and preferably about 80to about 50 mol %). It is particularly preferable to use about 20 toabout 50 mol % of asymmetric aromatic tetracarboxylic acid diester(s)and about 80 to about 50 mol % of symmetric aromatic tetracarboxylicacid diester(s).

The combined use of such symmetric and asymmetric aromatictetracarboxylic acid components is essential for the following reasons.Use of only symmetric aromatic tetracarboxylic acids and/or estersthereof induces crystallization of a polyimide film and thereby causespowderization of the film during heat treatment, which thus cannotachieve film formation. Although use of only asymmetric aromatictetracarboxylic acids and/or esters thereof achieves the formation of aseamless tubular PI film, such an obtained film has inferior yieldstress and elastic modulus, and, when used as a rotational belt, itsuffers from problems such as low driving responsiveness and earlyelongation of the belt.

In contrast, the combined use of aromatic tetracarboxylic acids and/oresters thereof at a mixing ratio as above achieves extremely highfilm-forming capability (formability), and provides a semi-conductiveseamless tubular PI film having high yield stress and elastic modulus.

Further, the addition of an asymmetric aromatic tetracarboxylic acidand/or ester thereof presumably causes a polyamic acid molecule to bend,thereby imparting flexibility.

The effects of the coexistence of asymmetric and symmetric aromatictetracarboxylic acids and/or esters thereof are most apparent when theyare mixed at a ratio as specified above.

Aromatic Diamine Component

Examples of aromatic diamine components include compounds having twoamino groups on a single aromatic ring (e.g., benzene nucleus), andcompounds having two amino groups in which two or more aromatic rings(e.g., benzene nuclei) are linked by a group such as —O—, —S—, —CO—,—CH₂—, —SO— or —SO₂—, or by a single bond. Specific examples thereofinclude p-phenylenediamine, o-phenylenediamine, m-phenylenediamine,4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl thioether,4,4′-diaminodiphenylcarbonyl, 4,4′-diaminodiphenylmethane, and1,4-bis(4-aminophenoxy)benzene. Among these, 4,4′-diaminodiphenyl etheris particularly preferable. Use of such an aromatic diamine componentallows the reaction to proceed more smoothly, and provides a film havinggreater toughness and higher heat resistance.

Organic Polar Solvent

An aprotic organic polar solvent is preferable as an organic polarsolvent used for a substantially monomeric mixed solution. Examplesthereof include N-methyl-2-pyrrolidone (hereafter referred to as “NMP”),N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide,dimethylsulfoxide, hexamethylphosphoramide, and1,3-dimethyl-2-imidazolidinone. Such solvents may be used singly, and amixed solvent of two or more such solvents can also be used. NMP isparticularly preferable. The amount of organic polar solvent is set toabout 65 to about 300 parts by weight (preferably about 80 to about 230parts by weight, and more preferably about 100 to about 200 parts byweight) per 100 parts by weight of the total amount of the aromatictetracarboxylic acid component and the aromatic diamine component(starting materials).

Carbon Black (CB)

In producing the semi-conductive tubular PI film of the invention, CBpowder is used in addition to the above-described components for thepurpose of imparting electrical resistance characteristics. The reasonfor using CB powder is that, compared with other known conductingmaterials such as metals and metal oxides, CB exhibits excellentdispersibility as well as excellent stability (change over time aftermixing and dispersion) in a prepared monomer mixed solution, and doesnot have any adverse effects on polycondensation.

There are various kinds of CB powder with various properties (electricalresistance, volatile content, specific surface area, particle diameter,pH value, DBP oil absorption, etc.) depending on the source (naturalgas, acetylene gas, coal tar, etc.) and production conditions(combustion conditions). CB powder having a developed structure with ahigh conductivity index (typically, CB powder produced by usingacetylene gas) is capable of providing a desired electrical resistanceeven when a comparatively small amount thereof is added, however, itsdispersibility upon mixing is inferior. With respect to oxidized CBpowder having low pH and CB powder with high volatile content, althoughtheir conductivity indices are not high and a relatively large amountmust be added to achieve a desired electrical resistance, theirdispersibility and storage stability are excellent, and a belt havinguniform electrical resistance can be obtained more easily therefrom.

Such conductive CB powder usually has a mean particle diameter of about15 to about 65 nm. When used, for example, for electrophotographicintermediate transfer belts for color printers, color copying machinesor the like, CB powder having a mean particle diameter of about 20 toabout 40 nm is particularly preferable.

Examples thereof include channel black and oxidized furnace black.Specific examples include Special Black 4 (pH 3, volatile content 14%,particle diameter 25 nm) and Special Black 5 (pH 3, volatile content15%, particle diameter 20 nm), manufactured by Degusa Corporation.

CB powder is added preferably in an amount of about 1 to about 35 partsby weight (and preferably about 5 to about 25 parts by weight) per 100parts by weight of the total amount of the aromatic tetracarboxylic acidcomponent and the aromatic diamine component, which are startingmaterials for a mixed solution in a substantially monomeric state.

The purpose of using CB powder in such an amount is to provide the filmwith volume resistivity (Ω·cm) (VR) and surface resistivity (Ω/sq) (SR)in a semi-conductive range. The lower limit is set at not less thanabout 1 part by weight because at least this amount is necessary toobtain sufficient conductivity. The upper limit is set at not more thanabout 35 parts by weight for the purpose of lowering the resistance andmaintaining formability to thereby prevent the film properties fromdeteriorating.

Preparation of Monomer Mixed Solution

A film-formation mixed solution in a substantially monomeric state(hereinafter sometimes referred as “monomer mixed solution”) is preparedby mixing specific amounts of aromatic tetracarboxylic acid component,aromatic diamine component, and organic polar solvent. The differencebetween the non-conductive tubular PI film and semi-conductive tubularPI film of the present invention is whether CB powder is contained, andthe monomer mixed solutions, which are staring materials therefor, areprepared under the same conditions in both cases. The preparationprocedure is not specifically limited. This is because, unlike whenhighly reactive aromatic tetracarboxylic dianhydrides are used, thearomatic tetracarboxylic acid components for use in the presentinvention do not substantially react with the diamine components at lowtemperatures (e.g., 30 to 40° C. or less), which is an advantage in thepreparation of a monomer mixed solution.

The monomer mixed solution is prepared by mixing and dissolving, in anorganic polar solvent, an aromatic tetracarboxylic acid component asabove and an aromatic diamine component as above at such a mixing ratiothat they are in approximately equimolar amounts. These components aremonomers, and are thus easily dissolvable in an organic polar solvent.Accordingly, they can be uniformly dissolved at a high concentration,and the obtained solution can be maintained in a substantially monomericstate. The present invention uses such a monomer mixed solution as astarting material.

Approximately equimolar amounts herein provide a mixing ratio at whichthe polycondensation reaction of an aromatic tetracarboxylic acidcomponent with an aromatic diamine component smoothly proceeds and adesired high-molecular-weight polyimide can be obtained. A substantiallymonomeric state herein means that almost all the components in the mixedsolution are in a monomeric state. The monomer mixed solution maycontain a small amount of low-molacular-weight polycondensate such asoligomer, within a range that the present invention is not adverselyaffected.

The amount of organic polar solvent is set to about 65 to about 300parts by weight (preferably about 80 to about 230 parts by weight, andmore preferably about 100 to about 200 parts by weight) per 100 parts byweight of the total amount of the aromatic tetracarboxylic acidcomponent and the aromatic diamine component (starting materials).Because the monomers can be easily dissolved in an organic polar solventas above, a mixed solution in a substantially monomeric state thusproduced provides the advantage that the amount of solvent can beminimized.

Examples of methods for preparing a monomer mixed solution are describedhereinafter.

According to a first example, symmetric and asymmetric aromatictetracarboxylic acid components in mol % as specified above are firstmixed and dissolved in an organic polar solvent. An aromatic diaminecomponent approximately equimolar to the total of these aromatictetracarboxylic acid components is then added to this solution whilestirring and uniformly dissolved therein, giving a film-formationmonomer mixed solution.

According to a second example, a solution of a specified amount ofsymmetric aromatic tetracarboxylic acid component and an approximatelyequimolar aromatic diamine component, and a solution of a specifiedamount of asymmetric aromatic tetracarboxylic acid component and anapproximately equimolar aromatic diamine component are preparedseparately. The solutions are then mixed at such a ratio that the twoaromatic tetracarboxylic acid components are each in mol % as specifiedabove, giving a film-formation monomer mixed solution.

According to a third example, specified amounts of symmetric andasymmetric aromatic tetracarboxylic acid components are added to anorganic polar solvent simultaneously with an aromatic diamine component,providing a uniform monomer mixed solution.

The monomer mixed solution for use in the invention may be ahigh-concentration solution having a nonvolatile content of about 45% byweight (particularly about 30 to about 45% by weight), unlikeconventional polyamic acid solutions having a maximum nonvolatilecontent of about 25% by weight. “Nonvolatile content” as used hereinmeans a content measured by the method described in the Examples. Use ofsuch a high-concentration monomer mixed solution leads to a speedypolymerization reaction, thereby enabling the reduction of filmformation time. Further, a thick film can be readily produced, and,because only a small amount of solvent is required, costs can be reducedand the evaporative removal of solvent can be simplified.

Additives such as imidazole compounds (e.g., 2-methylimidazole,1,2-dimethylimidazole, 2-methyl-4-methylimidazole,2-ethyl-4-ethylimidazole, and 2-phenylimidazole) and surfactants (e.g.,fluorosurfactants) can be added to the monomer mixed solution, withinranges that the effects of the present invention are not adverselyaffected.

A semi-conductive monomer mixed solution obtained by dispersing carbonblack in a monomer mixed solution is used in the production of asemi-conductive tubular PI film. The method for mixing CB powder in amonomer mixed solution is not limited, and stirring or like known methodcan be employed. A ball mill is preferably used for stirring, whereby afilm-formation semi-conductive monomer mixed solution having CBuniformly dispersed therein can be obtained.

Carbon black is used, as described above, in an amount of 1 to 35 partsby weight, and preferably 5 to 25 parts by weight, per 100 parts byweight of the total amount of the aromatic tetracarboxylic acidcomponent and the aromatic diamine component.

A-2. Method for Producing Seamless Tubular Polyimide Film

Hereinafter, a process of forming a tubular PI film using a monomermixed solution or semi-conductive monomer mixed solution as preparedabove is described. Although the below-described process uses a monomermixed solution, a process using a semi-conductive monomer mixed solutionmay be performed in the same manner.

Rotational molding using a rotating drum is employed for this formationprocess. First, a monomer mixed solution is introduced into a rotatingdrum and uniformly cast over the entire inner surface.

The method for introduction/casting may be such that, for example, amonomer mixed solution in an amount sufficient to provide the desiredfinal film thickness is introduced into a rotating drum whilestationary, and the rotational speed is then gradually raised to anextent that centrifugal force is generated, so that the solution is castuniformly over the entire inner surface by the centrifugal force.Alternatively, introduction/casting may be performed without usingcentrifugal force. According to one possible method, a horizontallyelongated slit-like nozzle is arranged inside a rotating drum, and,while slowly rotating the drum, the nozzle is rotated (at a speedgreater than the drum rotational speed). The film-formation monomermixed solution is uniformly ejected from the nozzle over the entireinner surface of the drum. The drum is mounted on rotating rollers, andis rotated indirectly by the rotation of the rollers.

A far-infrared radiation heater or the like is arranged around the drum,and heating is carried out indirectly by such an external heat source.The size of the drum depends on the size of the desired semi-conductivetubular PI film.

Heating is first carried out so that the inner surface of the drum isgradually heated to about 100 to about 190° C., and preferably to about110 to about 130° C. (first heating step). The rate of heating is about1 to about 2° C./min. This temperature is maintained for 30 to 120minutes, so that approximately half or more of the solvent is volatized,and a self-supporting tubular film is thereby formed. Althoughimidization requires a temperature of 280° C. or higher, if heating iscarried out at such a high temperature from the beginning, the polyimidebecomes highly crystalline, which adversely affects the CB dispersionstate, further causing problems such as a film thus formed lackingtoughness. Therefore, as a first heating step, the temperature is raisednot higher than about 190° C., and the polycondensation reaction iscompleted at such a temperature, so as to obtain a tough tubular PIfilm.

After this step, heating to complete imidization is then carried out asa second heating step at about 280 to about 400° C. (and preferablyabout 300 to about 380° C.). In this step, the temperature is alsopreferably raised from the temperature of the first heating stepgradually, rather than rapidly.

The second heating step may be performed while the seamless tubular filmis adhered to the inner surface of the rotating drum, or alternatively,it is also possible to separate and remove the seamless tubular filmfrom the rotating drum after the first heating step, and separately heatthe film to 280 to 400° C. by a heating means for imidization. Suchimidization usually takes about 2 to 3 hours. Accordingly, the entireprocess of the first and second heating steps usually takes about 4 toabout 7 hours in total.

A non-conductive (or semi-conductive) PI film of the invention is thusproduced. The film usually has a thickness of about 30 to about 200 μm,although not limited thereto, and preferably about 60 to about 120 μm.When used as an electrophotographic intermediate transfer belt, athickness of about 75 to about 100 μm is particularly preferable.

With respect to a semi-conductive PI film, the semiconductivity thereofis an electrical resistance property determined by the volumeresistivity (Ω·cm) (VR) and surface resistivity (Ω/sq) (SR). Such aproperty is due to CB powder having been mixed and dispersed therein.Basically, the resistivity can be freely varied by varying the amount ofCB powder to be mixed. The film of the invention may have, for example,a resistivity within the range of VR:10² to 10¹⁴ and SR:10³ to 10¹⁵, andpreferably VR:10⁶ to 10¹³ and SR:10⁷ to 10¹⁴. Such a resistivity rangecan be easily achieved by using CB powder in an amount as specifiedabove. The CB content of the film of the invention is usually about 5 toabout 25% by weight, and preferably about 8 to about 20% by weight.

The semi-conductive PI film of the invention has extremely uniformelectrical resistivity. More specifically, the semi-conductive PI filmof the invention is characterized by small variation in log surfaceresistivity SR and log volume resistivity VR; that is, their logstandard deviations of all the measurement points of the film are each0.2 or less, and preferably 0.15 or less. The film of the invention isalso characterized in that the difference in surface resistivities (interms of log) between its front and rear surfaces is as small as 0.4 orless, and preferably 0.2 or less. The film of the invention is furthercharacterized in that the value obtained by subtracting Log VR (logvolume resistivity) from Log SR (log surface resistivity) can bemaintained at a level as high as 1.0 to 3.0, and preferably 1.5 to 3.0.

The semi-conductive PI film of the invention is applicable to a widerange of uses due to its excellent electrical resistance properties andother characteristics. Examples of important applications that requirecharging characteristics include electrophotographic intermediatetransfer belts for color printers, color copying machines, or the like.Such a belt requires a semiconductivity (resistivity) of, for example,VR 10⁹ to 10¹² and SR 10¹⁰ to 10¹³, and accordingly, the semi-conductiveseamless tubular PI-based film of the invention is suitable.

The non-conductive or semi-conductive PI film of the invention is highlyefficient as a belt, and has high yield stress (σ_(Y)) and high tensilestrength (σ_(cr)). The yield stress (σ_(Y)) is 120 Mpa or more,particularly 120 to 160 Mpa, and the ratio of tensile strength to yieldstress (σ_(cr)/σ_(Y)) is 1.10 or more, particularly about 1.10 to about1.35.

B. SECOND EMBODIMENT

The electrically semi-conductive seamless tubular polyimide film(hereinafter sometimes referred to as “semi-conductive tubular PI film”)of the present invention is produced by rotationally molding asemi-conductive aromatic amic acid composition containing an aromaticamic acid oligomer, conductive carbon black (hereinafter sometimesreferred to as “CB”) and an organic polar solvent, and then imidizingthe resultant.

B-1. Semi-Conductive Aromatic Amic Acid Composition

The semi-conductive aromatic amic acid composition of the presentinvention is prepared by first subjecting approximately equimolaramounts of 1) at least two aromatic tetracarboxylic acid derivatives and2) at least one aromatic diamine to a partial polycondensation reactionin an organic polar solvent to obtain an aromatic amic acid oligomer (anaromatic amic acid having a number average molecular weight of about1000 to about 7000) solution, and then uniformly mixing conductivecarbon black powder with the aromatic amic acid oligomer solution.

(1) Aromatic Tetracarboxylic Acid Derivative

A mixture of at least one asymmetric aromatic tetracarboxylic acidderivative and at least one symmetric aromatic tetracarboxylic acidderivative are used as said at least two aromatic tetracarboxylic acidderivative starting materials.

Asymmetric Aromatic Tetracarboxylic Acid Derivative

Examples of asymmetric aromatic tetracarboxylic acid derivatives hereininclude asymmetric aromatic tetracarboxylic dianhydrides and asymmetricaromatic tetracarboxylic acid diesters (i.e., half esterified).

Examples of asymmetric aromatic tetracarboxylic acids include:

compounds in which four carboxyl groups are boundnon-point-symmetrically to a monocyclic or polycyclic aromatic ringsystem (e.g., benzene nucleus, naphthalene nucleus, biphenyl nucleus,and anthracene nucleus); and

compounds in which four carboxyl groups are boundnon-point-symmetrically to two monocyclic aromatic rings (e.g., benzenenuclei) linked by a group such as —CO—, —CH₂— or —SO₂—, or by a singlebond.

Specific examples of asymmetric aromatic tetracarboxylic acids include1,2,3,4-benzenetetracarboxylic acid, 1,2,6,7-naphthalenetetracarboxylicacid, 2,3,3′,4′-biphenyltetracarboxylic acid,2,3,3′,4′-benzophenonetetracarboxylic acid, 2,3,3′,4′-diphenyl ethertetracarboxylic acid, 2,3,3′,4′-diphenylmethanetetracarboxylic acid, and2,3,3′,4′-diphenylsulfonetetracarboxylic acid.

Examples of asymmetric aromatic tetracarboxylic dianhydrides hereininclude dianhydrides of such asymmetric aromatic tetracarboxylic acids.Specific examples thereof include compounds in which pairs of adjacentcarboxyl groups on one or more aromatic rings, in asymmetric aromatictetracarboxylic acids as above, form two acid anhydrides. Among these,2,3,3′,4′-biphenyltetracarboxylic dianhydride and1,2,6,7-naphthalenetetracarboxylic dianhydride are preferable, with2,3,3′,4′-biphenyltetracarboxylic dianhydride being particularlypreferable.

Examples of asymmetric aromatic tetracarboxylic acid diesters (i.e.,half esterified) for use in the present invention include diesters ofsuch asymmetric aromatic tetracarboxylic acids (i.e., half esterified).Specific examples thereof include compounds in which two of the fourcarboxyl groups of the asymmetric aromatic tetracarboxylic acid areesterified with one of each pair of adjacent carboxyl groups on anaromatic ring being esterified.

Examples of the two esters of such asymmetric aromatic tetracarboxylicacid diesters include di(lower alkyl)esters, and preferably di (C₁₋₃alkyl) esters, such as dimethyl esters, diethyl esters, and dipropylesters (particularly, dimethyl esters).

Among such symmetric aromatic tetracarboxylic acid diesters,2,3,3′,4′-biphenyltetracarboxylic acid dimethyl esters and2,3,3′,4′-biphenyltetracarboxylic acid diethyl esters are preferable,with 2,3,3′,4′-biphenyltetracarboxylic acid dimethyl esters beingparticularly preferable.

Asymmetric aromatic tetracarboxylic acid diesters as above arecommercially available, and can also be produced by known methods. Theycan be easily produced, for example, by a known method of reacting thecorresponding asymmetric aromatic tetracarboxylic dianhydride with thecorresponding alcohol (e.g., lower alcohol, preferably C₁₋₃alcohol) at amolar ratio of 1:2. By such a method, the acid anhydride, which is astarting material, reacts with the alcohol and thereby undergoes ringopening, providing a diester (half esterified) having an ester group anda carboxyl group on respective adjacent carbons on an aromatic ring.

Symmetric Aromatic Tetracarboxylic Acid Derivative

Symmetric aromatic tetracarboxylic acid derivatives herein includesymmetric aromatic tetracarboxylic dianhydrides and symmetric aromatictetracarboxylic acid diesters (i.e., half esterified).

Examples of symmetric aromatic tetracarboxylic acids include:

compounds in which four carboxyl groups are bound point-symmetrically toa monocyclic or polycyclic aromatic ring system (e.g., benzene nucleus,naphthalene nucleus, biphenyl nucleus, and anthracene nucleus); and

compounds in which four carboxyl groups are bound point-symmetrically totwo monocyclic aromatic rings (e.g., benzene nuclei) linked by a groupsuch as —CO—, —O—, —CH₂— or —SO₂—, or by a single bond.

Specific examples of symmetric aromatic tetracarboxylic acids include1,2,4,5-benzenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylicacid, 3,3′,4,4′-biphenyltetracarboxylic acid, 3,3′,4,4′-benzophenonetetracarboxylic acid, 3,3′,4,4′-diphenyl ether tetracarboxylic acid,3,3′,4,4′-diphenylmethanetetracarboxylic acid, and3,3′,4,4′-diphenylsulfonetetracarboxylic acid.

Examples of symmetric aromatic tetracarboxylic dianhydrides for use inthe present invention include dianhydrides of such symmetric aromatictetracarboxylic acids. Specific examples thereof include compounds inwhich pairs of adjacent carboxyl groups, in symmetric aromatictetracarboxylic acids as above, form two acid anhydride groups. Amongthese, 1,2,4,5-benzenetetracarboxylic dianhydride and3,3′,4,4′-biphenyltetracarboxylic dianhydride are preferable, with3,3′,4,4′-biphenyltetracarboxylic dianhydride being particularlypreferable. This is because these dianhydrides have beneficial effectson the resulting film strength and the like.

Examples of symmetric aromatic tetracarboxylic acid diesters (i.e., halfesterified) for use in the present invention include diesters of suchasymmetric aromatic tetracarboxylic acids as above (i.e., halfesterified). Specific examples thereof include compounds in which two ofthe four carboxyl groups of the symmetric aromatic tetracarboxylic acidare esterified with one of each pair of adjacent carboxyl groups on anaromatic ring being esterified.

Examples of the two esters of such symmetric aromatic tetracarboxylicacid diesters include di(lower alkyl)esters, and preferably C₁₋₃ alkylesters, such as dimethyl esters, diethyl esters, and dipropyl esters(particularly, dimethyl esters).

Among such symmetric aromatic tetracarboxylic acid diesters,3,3′,4,4′-biphenyltetracarboxylic acid dimethyl esters,3,3′,4,4′-biphenyltetracarboxylic acid diethyl esters, and2,3,5,6-benzenetetracarboxylic acid dimethyl esters are preferable, with3,3′,4,4′-biphenyltetracarboxylic acid dimethyl esters beingparticularly preferable.

Symmetric aromatic tetracarboxylic acid diesters as above arecommercially available, and can also be produced by known methods. Theycan be easily produced, for example, by reacting the correspondingsymmetric aromatic tetracarboxylic dianhydride with the correspondingalcohol (e.g., lower alcohol, preferably C₁₋₃ alcohol) at a molar ratioof 1:2. By such a method, the acid anhydride, which is a startingmaterial, reacts with the alcohol and thereby undergoes ring opening,providing a diester (half esterified) having an ester group and acarboxyl group on respective adjacent carbons on an aromatic ring.

Mixing Ratio

The mixing ratio for asymmetric and symmetric aromatic tetracarboxylicacid derivatives is specified such that the proportion of asymmetricaromatic tetracarboxylic acid derivative(s) is about 10 to about 55 mol% (preferably about 15 to about 55 mol %, and more preferably about 20to about 50 mol %) and the proportion of symmetric aromatictetracarboxylic acid derivative(s) is about 90 to about 45 mol %(preferably about 80 to about 45 mol %, and more preferably about 80 toabout 50 mol %). It is particularly preferable to use about 20 to about50 mol % of asymmetric aromatic tetracarboxylic dianhydride(s) and about80 to about 50 mol % of symmetric aromatic tetracarboxylicdianhydride(s).

The combined use of such symmetric and asymmetric aromatictetracarboxylic acid derivatives is essential for the following reasons.Use of only symmetric aromatic tetracarboxylic acid derivatives inducescrystallization of a polyimide film and thereby causes powderization ofthe film during heat treatment, which thus cannot achieve filmformation. Although use of only asymmetric aromatic tetracarboxylic acidderivatives achieves the formation of a seamless tubular PI film, suchan obtained film has inferior yield stress and elastic modulus, and,when used as a rotational belt, it suffers from problems such as lowdriving responsiveness and early elongation of the belt.

In contrast, the combined use of aromatic tetracarboxylic acidderivatives at a mixing ratio as above achieves extremely highfilm-forming capability (formability), and provides a semi-conductiveseamless tubular PI film having high yield stress and elastic modulus.

Further, the addition of an asymmetric aromatic tetracarboxylic acidderivative presumably causes a polyamic acid molecule to bend, therebyimparting flexibility.

The effects of the coexistence of such asymmetric and symmetric aromatictetracarboxylic acid derivatives are most apparent when they are mixedat a ratio as specified above.

(2) Aromatic Diamine

Examples of aromatic diamines include compounds having two amino groupson a single aromatic ring (e.g., benzene nucleus), and compounds havingtwo amino groups in which two or more aromatic rings (e.g., benzenenuclei) are linked by a group such as —O—, —S—, —CO—, —CH₂—, —SO— or—SO₂—, or by a single bond. Specific examples thereof includep-phenylenediamine, o-phenylenediamine, m-phenylenediamine,4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl thioether,4,4′-diaminodiphenylcarbonyl, 4,4′-diaminodiphenylmethane, and1,4-bis(4-aminophenoxy)benzene. Among these, 4,4′-diaminodiphenyl etheris particularly preferable. Use of such an aromatic diamine allows thereaction to proceed more smoothly, and provides a film having greatertoughness and higher heat resistance.

(3) Organic Polar Solvent

An aprotic organic polar solvent is preferable as an organic polarsolvent. Examples thereof include N-methyl-2-pyrrolidone (hereafterreferred to as “NMP”), N,N-dimethylformamide, N,N-diethylformamide,N,N-dimethylacetamide, dimethylsulfoxide, hexamethylphosphoramide, and1,3-dimethyl-2-imidazolidinone. Such solvents may be used singly, and amixed solvent of two or more such solvents can also be used. NMP isparticularly preferable. The amount of organic polar solvent is set toabout 100 to about 300 parts by weight (and preferably about 150 toabout 250 parts by weight) per 100 parts by weight of the total amountof the aromatic tetracarboxylic acid derivatives and the aromaticdiamine(s) (starting materials). An aromatic amic acid oligomer thusproduced can relatively easily dissolve in an organic polar solvent asabove, and accordingly is advantageous in that the amount of solventused can be minimized.

(4) Preparation of Aromatic Amic Acid Oligomer Solution

Examples of methods for preparing an aromatic amic acid oligomer (with anumber average molecular weight of about 1000 to about 7000) by apartial polycondensation reaction of at least two aromatictetracarboxylic acid derivatives with at least one organic diamine in anorganic polar solvent are described hereinafter.

According to a first example of an aromatic amic acid oligomerpreparation method, an aromatic amic acid oligomer (with a numberaverage molecular weight of about 1000 to about 7000) is prepared by apolycondensation reaction of at least two aromatic tetracarboxylicdianhydrides with an approximately equimolar amount of at least onearomatic diamine in an organic polar solvent at 80° C. or less.

Specifically, a mixture comprising about 15 to about 55 mol % (andpreferably about 20 to about 50 mol %) of asymmetric aromatictetracarboxylic dianhydride(s) and about 85 to about 45 mol % (andpreferably about 80 to about 50 mol %) of symmetric aromatictetracarboxylic dianhydride(s) is subjected to a polycondensationreaction. Usable organic polar solvents are those as described above.NMP is particularly preferable.

The purpose of limiting the temperature of the reaction to about 80° C.or less is to suppress imidization during the formation of the aromaticamic acid oligomer. A reaction temperature of 30 to 70° C. is morepreferable. A reaction temperature of more than 80° C. is not desirablein that polyimide is likely to be formed due to imidization. Thereaction time depends on the reaction temperature etc., and is usuallyabout a few hours to about 72 hours.

The molecular weight of the aromatic amic acid oligomer may becontrolled by any known method. The control may be suitably carried out,for example, by a method in which polymerization is carried out at anaromatic tetracarboxylic acid derivative/aromatic diamine molar ratio of0.5 to 0.95 to thereby obtain an aromatic amic acid oligomer having apredetermined molecular weight, and optionally further aromatictetracarboxylic acid derivative(s) is then added thereto so that thearomatic tetracarboxylic acid derivative/aromatic diamine becomesequimolar (see Japanese Examined Patent Publication No. 1989-22290); ora method in which a reaction is carried out at an approximatelyequimolar aromatic tetracarboxylic acid derivative/aromatic diamineratio, in the presence of a predetermined amount of compound thatsuppresses molecular weight increase, such as water (see Japanese PatentNo. 1990-3820).

According to a second example of an aromatic amic acid oligomerpreparation method, an aromatic amic acid oligomer (with a numberaverage molecular weight of about 1000 to about 7000) is produced by apolycondensation reaction of two or more aromatic tetracarboxylic aciddiesters with an equimolar amount of at least one aromatic diamine in anorganic polar solvent at about 90 to about 120° C.

Specifically, a mixture comprising about 15 to about 55 mol % (andpreferably about 20 to about 50 mol %) of asymmetric aromatictetracarboxylic acid diester(s) and about 85 to about 45 mol % (andpreferably about 80 to about 50 mol %) of symmetric aromatictetracarboxylic acid diester(s) is subjected to a polycondensationreaction. Usable organic polar solvents are those as described above.NMP is particularly preferable.

The temperature and time of the reaction are intimately related topreparing an aromatic amic acid oligomer with a desired molecularweight. The temperature of heating is usually about 90 to about 120° C.When the reaction temperature is in a high-temperature range, thereaction time is preferably short in order to reduce the yield of imide(imidization proportion) and suppress molecular weight increase. Heattreatment can be carried out by gradually heating to a predeterminedtemperature, performing the reaction at a predetermined temperature forabout 1 to about 3 hours, and then cooling. For example, the mixture maybe heated to about 90 to about 120° C. for about 1 to about 4 hours,allowed to react at the same temperature for about 30 minutes to about 2hours, and then cooled.

In the above first and second preparation methods, approximatelyequimolar amounts provide a mixing ratio at which an aromatic amic acidhaving a predetermined approximately oligomeric molecular weight,whereby a desired semi-conductive tubular PI film can be obtained.Heating may be performed (at, for example, about 40 to about 70° C.), ifnecessary, for such uniform dissolution of the components in an organicpolar solvent.

By such a first or second preparation method, an aromatic amic acidoligomer solution is prepared. The number average molecular weight (Mn)thereof is controlled to be about 1000 to about 7000 (preferably about3000 to about 7000). The reason for specifying such a range is that asolution having a number average molecular weight of 1000 or less (i.e.,monomer, dimer, etc.) does not achieve the desired effects onelectroconductive properties, while a solution having a number averagemolecular weight of 7000 or more is not usable because, for example, thesolution gelates due to the extreme lowering of oligomer solubility(see, e.g., Comparative Example B-1). The number average molecularweight can be measured by, for example, the method described in theExamples.

The aromatic amic acid oligomer has a controlled number averagemolecular weight (Mn) of about 1000 to about 7000, and the ratio (Mw/Mn)of the weight average molecular weight (Mw) to the number averagemolecular weight (Mn) is 2 or less.

An aromatic amic acid oligomer solution produced by such a heattreatment has an aromatic amic acid oligomer as the main component,which may have further partially reacted and imidized, etc. The yield ofimide (imidization proportion) in the aromatic amic acid oligomer ispreferably 30% or less, more preferably 25% or less, and particularlypreferably 20% or less. The yield of generated by-product imide(imidization proportion) can be measured by, for example, the methoddescribed in the Examples.

Further, the nonvolatile content of the aromatic amic acid oligomersolution may be controlled to be as high as about 30 to about 45% byweight. Control to such a high nonvolatile content is possible becausethe solution is oligomeric in which the molecular weight has not beenincreased and thus is easily dissolved in a solvent. Accordingly, athick film can be readily produced, and, because only a small amount ofsolvent is required, costs can be reduced and the evaporative removal ofsolvent can be simplified. “Nonvolatile content” as used herein means acontent measured by the method described in the Example B-1.

(5) Preparation of Semi-Conductive Aromatic Amic Acid Composition

An aromatic amic acid oligomer solution thus obtained is uniformly mixedwith conductive CB powder, providing a semi-conductive aromatic amicacid composition.

The reason for using CB powder for imparting electrical resistanceproperties is that, compared with other known conducting materials suchas metals and metal oxides, CB exhibits excellent dispersibility as wellas excellent stability (change over time after mixing and dispersion) ina prepared monomer mixed solution, and does not have any adverse effectson polycondensation.

There are various kinds of CB powder with various properties (electricalresistance, volatile content, specific surface area, particle diameter,pH value, DBP oil absorption, etc.) depending on the source (naturalgas, acetylene gas, coal tar, etc.) and production conditions(combustion conditions). It is desirable to employ CB powder that iscapable of stably providing a desired electrical resistance withoutvariation even when a minimum amount thereof is mixed and dispersed.

Such conductive CB powder usually has a mean particle diameter of about15 to about 65 nm. When used, for example, for electrophotographicintermediate transfer belts for color printers, color copying machinesor the like, CB powder having a mean particle diameter of about 20 toabout 40 nm is particularly preferable.

Examples thereof include channel black and oxidized furnace black.Specific examples include Special Black 4 (pH 3, volatile content 14%,particle diameter 25 nm) and Special Black 5 (pH 3, volatile content15%, particle diameter 20 nm), manufactured by Degusa Corporation.

The method for mixing CB powder into an aromatic amic acid oligomersolution is not limited as long as such CB powder can be uniformly mixedand dispersed in the aromatic amic acid oligomer solution. For example,ball mills, sand mills, and ultrasonic mills are usable.

CB powder is added preferably in an amount of about 3 to about 30 partsby weight (and preferably about 10 to about 25 parts by weight) per 100parts by weight of the total amount of the aromatic tetracarboxylic acidderivatives and the organic diamine(s), which are starting materials forthe aromatic amic acid oligomer.

The purpose of using CB powder in such an amount is to provide the filmwith volume resistivity (VR) and surface resistivity (SR) in asemi-conductive range. The lower limit is set at not less than about 3parts by weight because at least this amount is necessary to obtainsufficient conductivity. The upper limit is set at not more than about30 parts by weight for the purpose of lowering the resistance andmaintaining formability to thereby prevent the film properties fromdeteriorating.

The semi-conductive aromatic amic acid composition has a nonvolatilecontent of about 30 to about 45% by weight. The nonvolatile matter has aCB powder content of about 3 to about 25% by weight (and preferablyabout 10 to about 20% by weight), and an aromatic amic acidoligomer-derived nonvolatile content of about 75 to about 97% by weight(and preferably about 80 to about 90% by weight).

Additives such as imidazole compounds (e.g., 2-methylimidazole,1,2-dimethylimidazole, 2-methyl-4-methylimidazole,2-ethyl-4-ethylimidazole, and 2-phenylimidazole) and surfactants (e.g.,fluorosurfactants) can be added to the composition, within ranges thatthe effects of the present invention are not adversely affected.

A film-formation semi-conductive aromatic amic acid composition isthereby produced, in which CB powder is uniformly dispersed.

B-2. Semi-Conductive Seamless Tubular Polyimide Film

Hereinafter, a process of forming a semi-conductive tubular polyimidefilm using a semi-conductive aromatic amic acid composition as preparedabove is described.

Rotational molding using a rotating drum is employed for this formationprocess. First, a semi-conductive aromatic amic acid composition isintroduced into a rotating drum and uniformly cast over the entire innersurface.

The method for introduction/casting may be such that, for example, asemi-conductive aromatic amic acid composition in an amount sufficientto provide the desired final film thickness is introduced into arotating drum while stationary, and the rotational speed is thengradually raised to an extent that centrifugal force is generated, sothat the composition is cast uniformly over the entire inner surface bythe centrifugal force. Alternatively, introduction/casting may beperformed without using centrifugal force. According to one possiblemethod, a horizontally elongated slit-like nozzle is arranged inside arotating drum, and, while slowly rotating the drum, the nozzle isrotated (at a speed greater than the drum rotational speed). Thefilm-formation semi-conductive aromatic amic acid composition isuniformly ejected from the nozzle over the entire inner surface of thedrum.

In both methods, the rotating drum has its inner surfacemirror-finished, and a barrier is arranged at the periphery of each endto prevent fluid leakage. The drum is mounted on rotating rollers, andis rotated indirectly by the rotation of the rollers.

A far-infrared radiation heater or the like is arranged around the drum,and heating is carried out indirectly by such an external heat source.The size of the drum depends on the size of the desired semi-conductivetubular PI film.

Heating is first carried out so that the inner surface of the drum isgradually heated to about 100 to about 190° C., and preferably to about110 to about 130° C. (first heating step). The rate of heating is about1 to about 2° C./min. This temperature is maintained for 1 to 2 hours,so that approximately half or more of the solvent is volatized, and aself-supporting tubular film is thereby formed. Although imidizationrequires a temperature of 280° C. or higher, if heating is carried outat such a high temperature from the beginning, the polyimide becomeshighly crystalline, which adversely affects the CB dispersion state,further causing problems such as a film thus formed lacking toughness.Therefore, as a first heating step, the temperature is raised not higherthan about 190° C., and the polycondensation reaction is completed atsuch a temperature, so as to obtain a tough tubular PI film.

After this step, heating to complete imidization is then carried out asa second heating step at about 280 to about 400° C. (and preferablyabout 300 to about 380° C.). In this step, the temperature is alsopreferably raised from the temperature of the first heating stepgradually, rather than rapidly.

The second heating step may be performed while the seamless tubular filmis adhered to the inner surface of the rotating drum, or alternatively,it is also possible to separate and remove the seamless tubular filmfrom the rotating drum after the first heating step, and separately heatthe film to 280 to 400° C. by a heating means for imidization. Suchimidization usually takes about 2 to 3 hours. Accordingly, the entireprocess of the first and second heating steps usually takes about 4 toabout 7 hours in total.

A semi-conductive seamless tubular PI film of the invention is thusproduced. The film usually has a thickness of about 50 to about 150 μm,although not limited thereto, and preferably about 60 to about 120 μm.When used as an electrophotographic intermediate transfer belt, athickness of about 75 to about 100 μm is particularly preferable.

The semiconductivity of the film is an electrical resistance propertydetermined by the volume resistivity (Ω·cm) (hereinafter referred to as“VR”) and surface resistivity (Ω/sq) (hereinafter referred to as “SR”).Such a property is due to CB powder having been mixed and dispersedtherein. Basically, the resistivity can be freely varied by varying theamount of CB powder to be mixed. The film of the invention may have, forexample, a resistivity within the range of VR:10² to 10¹⁴ and SR:10³ to10¹⁵, and preferably VR:10⁶ to 10¹³ and SR:10⁷ to 10¹⁴. Such aresistivity range can be easily achieved by using CB powder in an amountas specified above. The CB content of the film of the invention isusually about 3 to about 25% by weight, and preferably about 10 to about20% by weight.

The semi-conductive PI film of the invention has extremely uniformelectrical resistivity. More specifically, the semi-conductive PI filmof the invention is characterized by small variation in log surfaceresistivity SR and log volume resistivity VR; that is, their logstandard deviations of all the measurement points of the film are each0.2 or less, and preferably 0.15 or less. The film of the invention isalso characterized in that the difference in surface resistivities (interms of log) between its front and rear surfaces is as small as 0.4 orless, and preferably 0.2 or less. The film of the invention is furthercharacterized in that the value obtained by subtracting Log VR (logvolume resistivity) from Log SR (log surface resistivity) can bemaintained at a level as high as 1.0 to 3.0, and preferably 1.3 to 3.0.

Such excellent electrical characteristics of the PI film of the presentinvention are attributed to the use in its production of asemi-conductive aromatic amic acid composition, which has an “aromaticamic acid oligomer” and CB powder mixed therein. More specifically, thereason for such excellent electrical characteristics is presumably thatthe composition has CB powder uniformly dispersed with an aromatic amicacid oligomer, and, during film production, polymerization of thecomposition can proceed while maintaining such a uniform dispersion.

The PI film of the invention is applicable to a wide range of uses dueto its excellent electrical resistance properties and othercharacteristics. Examples of important applications that requireelectrostatic properties include electrophotographic intermediatetransfer belts for color printers, color copying machines, or the like.Such a belt requires a semiconductivity (resistivity) of, for example,VR 10⁹ to 10¹² and SR 10¹⁰ to 10¹³, and accordingly, the semi-conductiveseamless tubular PI film of the invention is suitable.

The semi-conductive PI film of the invention is highly efficient as abelt, and has high yield stress (σ_(Y)) and high tensile strength(σ_(cr)). The yield stress (σ_(Y)) is 120 Mpa or more, particularly 120to 160 Mpa, and the ratio of tensile strength to yield stress(σ_(cr)/σ_(Y)) is 1.10 or more, particularly about 1.10 to about 1.35.

C. THIRD EMBODIMENT

The electrically semi-conductive seamless tubular polyimide-based film(hereinafter sometimes referred to as “semi-conductive tubular PI-basedfilm”) of the present invention is produced by rotationally molding andheat treating (imidizing) a semi-conductive polyimide-based precursorcomposition (hereinafter sometimes referred to as “semi-conductive PIprecursor composition”).

C-1. Semi-Conductive Polyimide-Based Precursor Composition

The semi-conductive polyimide-based precursor composition of the presentinvention is produced by first dissolving approximately equimolaramounts of 1) at least two aromatic tetracarboxylic acid diesters and 2)at least one aromatic diamine in an organic polar solvent to obtain anylon salt-type monomer solution, then mixing a high-molecular-weightpolyimide precursor solution or a high-molecular-weight polyamideimidesolution with the nylon salt-type monomer solution to prepare a mixedsolution, and then uniformly dispersing carbon black (hereinaftersometimes referred to as “CB”) in the mixed solution.

(1) Aromatic Tetracarboxylic Acid Diesters (Half Esterified)

A mixture of at least one asymmetric aromatic tetracarboxylic aciddiester and at least one symmetric aromatic tetracarboxylic acid diesteris used as said at least two aromatic tetracarboxylic acid diesterstarting materials.

Asymmetric aromatic tetracarboxylic acid diesters for use in the presentinvention are explained hereinafter.

Examples of asymmetric aromatic tetracarboxylic acids include:

compounds in which four carboxyl groups are boundnon-point-symmetrically to a monocyclic or polycyclic aromatic ringsystem (e.g., benzene nucleus, naphthalene nucleus, biphenyl nucleus,and anthracene nucleus); and

compounds in which four carboxyl groups are boundnon-point-symmetrically to two monocyclic aromatic rings (e.g., benzenenuclei) linked by a group such as —CO—, —CH₂— or —SO₂—, or by a singlebond.

Specific examples of asymmetric aromatic tetracarboxylic acids include1,2,3,4-benzenetetracarboxylic acid, 1,2,6,7-naphthalenetetracarboxylicacid, 2,3,3′,4′-biphenyltetracarboxylic acid,2,3,3′,4′-benzophenonetetracarboxylic acid, 2,3,3′,4′-diphenyl ethertetracarboxylic acid, 2,3,3′,4′-diphenylmethanetetracarboxylic acid, and2,3,3′,4′-diphenylsulfonetetracarboxylic acid.

Examples of asymmetric aromatic tetracarboxylic acid diesters (i.e.,half esterified) for use in the present invention include diesters ofsuch asymmetric aromatic tetracarboxylic acids. Specific examplesthereof include compounds in which two of the four carboxyl groups ofthe asymmetric aromatic tetracarboxylic acid are esterified with one ofeach pair of adjacent carboxyl groups on an aromatic ring beingesterified.

Examples of the two esters of such asymmetric aromatic tetracarboxylicacid diesters include di(lower alkyl)esters, and preferably C₁₋₃ alkylesters, such as dimethyl esters, diethyl esters, and dipropyl esters(particularly, dimethyl esters).

Among such asymmetric aromatic tetracarboxylic acid diesters,2,3,3′,4′-biphenyltetracarboxylic acid dimethyl esters and2,3,3′,4′-biphenyltetracarboxylic acid diethyl esters are preferable,with 2,3,3′,4′-biphenyltetracarboxylic acid dimethyl esters beingparticularly preferable.

Asymmetric aromatic tetracarboxylic acid diesters as above arecommercially available, and can also be produced by known methods. Theycan be easily produced, for example, by reacting the correspondingasymmetric aromatic tetracarboxylic dianhydride with the correspondingalcohol (e.g., lower alcohol, preferably C₁₋₃ alcohol) at a molar ratioof 1:2. By such a method, the acid anhydride, which is a startingmaterial, reacts with the alcohol and thereby undergoes ring opening,providing a diester (half esterified) having an ester group and acarboxyl group on respective adjacent carbons on an aromatic ring.

Symmetric aromatic tetracarboxylic acid diesters for use in the presentinvention are explained hereinafter.

Examples of symmetric aromatic tetracarboxylic acids include:

compounds in which four carboxyl groups are bound point-symmetrically toa monocyclic or polycyclic aromatic ring system (e.g., benzene nucleus,naphthalene nucleus, biphenyl nucleus, and anthracene nucleus); and

compounds in which four carboxyl groups are bound point-symmetrically totwo monocyclic aromatic rings (e.g., benzene nuclei) linked by a groupsuch as —CO—, —O—, —CH₂— or —SO₂—, or by a single bond.

Specific examples of symmetric aromatic tetracarboxylic acids include1,2,4,5-benzenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylicacid, 3,3′,4,4′-biphenyltetracarboxylic acid, 3,3′,4,4′-benzophenonetetracarboxylic acid, 3,3′,4,4′-diphenyl ether tetracarboxylic acid,3,3′,4,4′-diphenylmethanetetracarboxylic acid, and3,3′,4,4′-diphenylsulfonetetracarboxylic acid.

Examples of symmetric aromatic tetracarboxylic acid diesters (i.e., halfesterified) for use in the present invention include diesters of suchsymmetric aromatic tetracarboxylic acids (i.e., half esterified).Specific examples thereof include compounds in which two of the fourcarboxyl groups of the symmetric aromatic tetracarboxylic acid areesterified with one of each pair of adjacent carboxyl groups on anaromatic ring being esterified.

Examples of the two esters of such symmetric aromatic tetracarboxylicacid diesters include di(lower alkyl)esters, and preferably C₁₋₃ alkylesters, such as dimethyl esters, diethyl esters, and dipropyl esters(particularly, dimethyl esters).

Among such symmetric aromatic tetracarboxylic acid diesters,3,3′,4,4′-biphenyltetracarboxylic acid dimethyl esters,3,3′,4,4′-biphenyltetracarboxylic acid diethyl esters,1,2,4,5-benzenetetracarboxylic acid dimethyl esters, and1,2,4,5-benzenetetracarboxylic acid diethyl esters are preferable, with3,3′,4,4′-biphenyltetracarboxylic acid dimethyl esters beingparticularly preferable.

Symmetric aromatic tetracarboxylic acid diesters as above arecommercially available, and can also be produced by known methods. Theycan be easily produced, for example, by a known method of reacting thecorresponding symmetric aromatic tetracarboxylic dianhydride with thecorresponding alcohol (e.g., lower alcohol, preferably C₁₋₃ alcohol) ata molar ratio of 1:2. By such a method, the acid anhydride, which is astarting material, reacts with the alcohol and thereby undergoes ringopening, providing a diester (half esterified) having an ester group anda carboxyl group on respective adjacent carbons on an aromatic ring.

The mixing ratio for asymmetric and symmetric aromatic tetracarboxylicacid diesters is specified such that the proportion of asymmetricaromatic tetracarboxylic acid diester(s) is about 10 to about 50 mol %(and preferably about 20 to about 40 mol %) and the proportion ofsymmetric aromatic tetracarboxylic acid diester(s) is about 90 to about50 mol % (and preferably about 80 to about 60 mol %). It is particularlypreferable to use about 20 to about 30 mol % of asymmetrictetracarboxylic aromatic acid diester(s) and about 70 to about 80 mol %of symmetric aromatic tetracarboxylic acid diester(s).

The combined use of such symmetric and asymmetric aromatictetracarboxylic acid diesters is essential for the following reasons.Use of only symmetric aromatic tetracarboxylic acid diesters inducescrystallization of a polyimide film and thereby causes powderization ofthe film during heat treatment, which thus cannot achieve filmformation. Although use of only asymmetric aromatic tetracarboxylic acidderivatives achieves the formation of a seamless tubular PI film, suchan obtained film has inferior yield stress and elastic modulus, and,when used as a rotational belt, it suffers from problems such as lowdriving responsiveness and early elongation of the belt.

In contrast, the use of mixed aromatic tetracarboxylic acid diestersachieves extremely high film-forming capability (formability), andprovides a semi-conductive seamless tubular PI film having high yieldstress and elastic modulus.

Further, the addition of an asymmetric aromatic tetracarboxylic aciddiester presumably causes a polyamic acid molecule to bend, therebyimparting flexibility.

The effects of the coexistence of such asymmetric and symmetric aromatictetracarboxylic acid derivatives are most apparent when they are mixedat a ratio as specified above.

(2) Aromatic Diamine

Examples of aromatic diamines include compounds having two amino groupson a single aromatic ring (e.g., benzene nucleus), and compounds havingtwo amino groups in which two or more aromatic rings (e.g., benzenenuclei) are linked by a group such as —O—, —S—, —CO—, —CH₂—, —SO— or—SO₂—, or by a single bond. Specific examples thereof includep-phenylenediamine, o-phenylenediamine, m-phenylenediamine,4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl thioether,4,4′-diaminodiphenylcarbonyl, 4,4′-diaminodiphenylmethane, and1,4-bis(4-aminophenoxy)benzene. Among these, 4,4′-diaminodiphenyl etheris particularly preferable. Use of such an aromatic diamine allows thereaction to proceed more smoothly, and provides a film having greatertoughness and higher heat resistance.

(3) Nylon Salt-Type Monomer Solution

At least two aromatic tetracarboxylic acid diesters as above and anequimolar amount of at least one aromatic diamine as above are uniformlymixed in an organic polar solvent, providing a nylon salt-type monomersolution. Heating may be performed (at, for example, about 40 to about70° C.), if necessary, for such uniform dissolution of the components inan organic polar solvent.

An aprotic organic polar solvent is preferable as an organic polarsolvent. Examples thereof include N-methyl-2-pyrrolidone (hereafterreferred to as “NMP”), N,N-dimethylformamide, N,N-diethylformamide,N,N-dimethylacetamide, dimethylsulfoxide, hexamethylphosphoramide, and1,3-dimethyl-2-imidazolidinone.

Such solvents may be used singly, and a mixed solvent of two or moresuch solvents can also be used. NMP is particularly preferable. Theamount of organic polar solvent is set to about 100 to about 300 partsby weight (and preferably about 120 to about 200 parts by weight) per100 parts by weight of the total amount of said at least two aromatictetracarboxylic acid diesters and said at least one aromatic diamine(starting materials).

Such a nylon salt-type monomer solution presumably has a constitution inwhich, for example, ion pairs of carboxylate ions of the aromatictetracarboxylic acid diesters and ammonium ions of the aromatic diamineare present in a substantially monomeric state in an organic polarsolvent (see, e.g., the formula given below). Further, such ions can bedissolved in an organic polymer solvent as above extremely easilybecause of their substantially monomeric state, thus providing theadvantage that the amount of solvent used can be minimized.

(Ar is a tetravalent residue obtained by removing two carboxyl groupsand two ester groups from an aromatic tetracarboxylic acid, Ar′ is adivalent residue obtained by removing two amino groups from an aromaticdiamine, and R is an alkyl group)(4) High-Molecular-Weight Polymide Precursor Solution andHigh-Molecular-Weight Polyamideimide Solution

A polyamic acid solution having a number average molecular weight of10000 or more is used as the high-molecular-weight polymide precursorsolution, and a polyamideimide solution having a number averagemolecular weight of 10000 or more is used as the high-molecular-weightpolyamideimide solution. A number average molecular weight as usedherein is a value measured by GPC (solvent :NMP, calculated withreference to polyethylene oxide).

Polyamic Acid Solution

A polyamic acid solution having a number average molecular weight of10000 or more is produced, for example, by a known method using, asstarting materials, a biphenyl tetracarboxylic dianhydride and adiaminodiphenyl ether component in an organic polar solvent. Usableorganic-polar solvents are those described above for use in a nylonsalt-type monomer solution.

Examples of biphenyl tetracarboxylic dianhydrides include2,3,3′,4′-biphenyl tetracarboxylic dianhydride (a-BPDA),3,3′,4,4′-biphenyl tetracarboxylic dianhydride (s-BPDA), and2,2′,3,3′-biphenyl tetracarboxylic dianhydride.

Examples of diaminodiphenyl ether components include4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether, and 3,4′-diaminodiphenyl ether.

Such a biphenyl tetracarboxylic dianhydride and diaminodiphenyl ethercomponent are mixed in approximately equimolar amounts. A known methodcan be employed for the polycondensation reaction thereof. An examplethereof is a method for preparing a polyamic acid solution, in which abiphenyl tetracarboxylic acid component is added to a solutioncontaining a diaminodiphenyl ether component at room temperature (about15 to about 30° C.) and thereby amidated. Such an obtained polyamic acidhas a number average molecular weight of 10000 or more, and preferably12000 to 20000.

Polyamideimide Solution

A polyamideimide solution having a number average molecular weight of10000 or more is produced by a known reaction, such as polycondensationof an acid anhydride component comprising trimellitic anhydride andbenzophenonetetracarboxylic anhydride with an aromatic isocyanate in anorganic solvent. Usable organic polar solvents are those described abovefor use in a nylon salt-type monomer solution.

The acid anhydride component has a trimellitic anhydride proportion ofabout 70 to about 95 mol %, and a benzophenonetetracarboxylic anhydrideproportion of about 5 to about 30 mol %.

Examples of aromatic isocyanates include bitolylene diisocyanate,3,3′-diphenylsulfone diisocyanate, isophorone diisocyanate,1,4-diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, m-xylenediisocyanate, p-xylene diisocyanate, and 1,4-cyclohexylene diisocyanate.

Such an aromatic isocyanate is used in such an amount that the totalnumber of aromatic isocyanate groups is equivalent to the total numberof carboxyl groups and acid anhydride groups of the acid component.

Such polyamideimide has a number average molecular weight of 10000 ormore, and preferably about 15000 to about 20000.

(5) Mixed Solution

A nylon salt-type monomer solution as above and a high-molecular-weightpolymide precursor solution or high-molecular-weight polyamideimidesolution as above are mixed, providing a mixed solution. A known method,such as a propeller mixer, magnetic stirrer, or pot mill, can beemployed for this mixing.

They are preferably mixed in such amounts (ratio) that thehigh-molecular-weight polymide precursor solution (in particular, apolyamic acid solution having a number average molecular weight of 10000or more) or the high-molecular-weight polyamideimide solution(polyamideimide solution having a number average molecular weight of10000 or more) has about 10 to about 50 parts by weight (and preferablyabout 20 to about 30 parts by weight) of nonvolatile matter per 100parts by weight of the nonvolatile matter of the nylon salt-type monomersolution. “Nonvolatile matter” herein is as measured by the methoddescribed in Example C-1.

When the high-molecular-weight polymide precursor solution orhigh-molecular-weight polyamideimide solution has less than 10 parts byweight of nonvolatile matter per 100 parts by weight of the nonvolatilematter of the nylon salt-type monomer solution, it becomes difficult toachieve the effects of the present invention. When the nonvolatilematter is more than 50 parts by weight and carbon black is added to sucha solution, rate of viscosity increase becomes remarkably high andpulverization of the carbon black becomes difficult, and as a result,the addition of a large amount of organic polar solvent is required,thereby reducing production efficiency.

(6) Semi-Conductive PI Precursor Composition

Conductive CB powder is uniformly dispersed in such a mixed solution,providing a semi-conductive PI precursor composition.

The reason for using CB powder for imparting electrical resistanceproperties is that (compared with other known conducting materials suchas metals and metal oxides) CB exhibits excellent dispersibility as wellas excellent stability (change over time after mixing and dispersion) ina prepared monomer mixed solution, and does not have any adverse effectson polycondensation.

There are various kinds of CB powder with various properties (electricalresistance, volatile content, specific surface area, particle diameter,pH value, DBP oil absorption, etc.) depending on the source (naturalgas, acetylene gas, coal tar, etc.) and production conditions(combustion conditions). It is desirable to employ CB powder that iscapable of stably providing a desired electrical resistance withoutvariation even when a minimum amount thereof is mixed and dispersed.

Such conductive CB powder usually has a mean particle diameter of about15 to about 65 nm. When used, for example, for electrophotographicintermediate transfer belts for color printers, color copying machinesor the like, CB powder having a mean particle diameter of about 20 toabout 40 nm is particularly preferable.

Carbon black having a high conductivity index, such as ketjen black andacetylene black, is likely to lead to the formation of secondaryaggregation (structure) and the occurrence of a conductivity chain, andaccordingly, control within the semi-conductive region is difficult.Therefore, use of acidic. carbon black, which is unlikely to lead tosuch structure formation, is effective.

Examples thereof include channel black and oxidized furnace black.Specific examples include Special Black 4 (pH 3, volatile content 14%,particle diameter 25 nm) and Special Black 5 (pH 3, volatile content15%, particle diameter 20 nm), manufactured by Degusa Corporation.

The method for mixing CB powder is not limited as long as such CB powdercan be uniformly mixed and dispersed in the mixed solution. For example,ball mills, sand mills, and ultrasonic mills are usable.

CB powder is added preferably in an amount of about 5 to about 40 partsby weight (and preferably about 10 to about 30 parts by weight) per 100parts by weight of the total amount of: 1) aromatic tetracarboxylic aciddiester and organic diamine, which are starting materials for the nylonsalt-type monomer; and 2) acid anhydride and diamine, which are startingmaterials for the high-molecular-weight polyimide precursor, or acidanhydrides and aromatic isocyanate, which are starting materials for thehigh-molecular-weight polyamideimide. The purpose of using CB powder insuch an amount is to provide the film with volume resistivity (VR) andsurface resistivity (SR) in a semi-conductive range. The lower limit isset at not less than about 5 parts by weight because at least thisamount is necessary to obtain sufficient conductivity. The upper limitis set at not more than about 40 parts by weight for the purpose oflowering the resistance and maintaining formability to thereby preventthe film properties from deteriorating.

The semi-conductive PI precursor composition has a nonvolatile contentof about 20 to about 60% by weight, and this nonvolatile matter has a CBpowder content of about 5 to about 30% by weight (and preferably about 9to about 23% by weight). “Nonvolatile content” as used herein means acontent measured by the method described in Example C-1.

Additives such as imidazole compounds (e.g., 2-methylimidazole,1,2-dimethylimidazole, 2-methyl-4-methylimidazole,2-ethyl-4-ethylimidazole, and 2-phenylimidazole) and surfactants (e.g.,fluorosurfactants) can be added to the composition, within ranges thatthe effects of the present invention are not adversely affected.

A film-formation semi-conductive PI precursor composition is therebyproduced, in which CB powder is uniformly dispersed.

By mixing a high-molecular-weight polymide precursor solution or ahigh-molecular-weight polyamideimide solution with a nylon salt-typemonomer, the storage stability of the uniform dispersion of carbon blackin the semi-conductive PI precursor composition of the present inventionis remarkably improved. Further, a conductive tubular polyimide-basedfilm formed by rotationally molding such a semi-conductive PI precursorcomposition has excellent electrical conductivity, i.e., extremelystable and uniform electrical resistivity in the thickness direction.The reasons for this are not certain but are presumably that, because apolymer having a relatively high number average molecular weight ispresent in the polyimide-based precursor composition, the aggregation ofcarbon black is suppressed by physical entanglement between the polymercomponent and carbon black and also by the viscosity of the polymer.Furthermore, presumably, the polymer's viscosity alleviates the effectson carbon black particles caused by centrifugal force during rotationalmolding, and also alleviates the effects caused by thermal convection orevaporative convection during the volatilization of solvent, andmoreover, the reaction rate of heat-induced polymerization can bemoderated.

C-2. Conductive Seamless Tubular Polyimide-Based Film

Hereinafter, a process of forming a conductive tubular PI-based filmusing a semi-conductive PI precursor composition as prepared above isdescribed.

Rotational molding using a rotating drum is employed for this formationprocess. First, a semi-conductive PI precursor composition is introducedinto a rotating drum and uniformly cast over the entire inner surface.

The method for introduction/casting may be such that, for example, asemi-conductive PI precursor composition in an amount sufficient toprovide the desired final film thickness is introduced into a rotatingdrum while stationary, and the rotational speed is then gradually raisedto an extent that centrifugal force is generated. The composition iscast uniformly over the entire inner surface by the centrifugal force.Alternatively, introduction/casting may be performed without usingcentrifugal force. According to one possible method, a horizontallyelongated slit-like nozzle is arranged inside a rotating drum, and,while slowly rotating the drum, the nozzle is rotated (at a speedgreater than the drum rotational speed). The film-formationsemi-conductive PI precursor composition is uniformly ejected from thenozzle over the entire inner surface of the drum.

In both methods, the rotating drum has its inner surfacemirror-finished, and a barrier is arranged at the periphery of each endto prevent fluid leakage. The drum is mounted on rotating rollers, andis rotated indirectly by the rotation of the rollers.

A far-infrared radiation heater or the like is arranged around the drum,and heating is carried out indirectly by such an external heat source.The size of the drum depends on the size of the desired semi-conductivetubular PI film.

Heating is first carried out so that the inner surface of the drum isgradually heated to about 100 to about 190° C., and preferably to about110 to about 130° C. (first heating step). The rate of heating is about1 to about 2° C./min. This temperature is maintained for 1 to 3 hours,so that approximately half or more of the solvent is volatized, and aself-supporting tubular film is thereby formed. Although imidizationrequires a temperature of 280° C. or higher, if heating is carried outat such a high temperature from the beginning, the polyimide becomeshighly crystalline, which adversely affects the CB dispersion state,further causing problems such as a film thus formed lacking toughness.Therefore, as a first heating step, the temperature is raised not higherthan about 190° C., and the polycondensation reaction is completed atsuch a temperature, so as to obtain a tough tubular PI film.

After this step, heating to complete imidization is then carried out asa second heating step at about 280 to about 400° C. (and preferablyabout 300 to about 380° C.). In this step, the temperature is alsopreferably raised from the temperature of the first heating stepgradually, rather than rapidly.

The second heating step may be performed while the seamless tubular filmis adhered to the inner surface of the rotating drum, or alternatively,it is also possible to separate and remove the seamless tubular filmfrom the rotating drum after the first heating step, and separately heatthe film to 280 to 400° C. by a heating means for imidization. Suchimidization usually takes about 2 to 3 hours. Accordingly, the entireprocess of the first and second heating steps usually takes about 4 toabout 7 hours in total.

A conductive seamless tubular PI film of the invention is thus produced.The film usually has a thickness of about 30 to about 200 μm, althoughnot limited thereto, and preferably about 50 to about 120 μm. When usedas an electrophotographic intermediate transfer belt, a thickness ofabout 70 to about 100 μm is particularly preferable.

The semiconductivity of the film is an electrical resistance propertydetermined by the volume resistivity (Ω·cm) (hereinafter referred to as“VR”) and surface resistivity (Ω/sq) (hereinafter referred to as “SR”).Such a property is due to CB powder having been mixed and dispersedtherein. Basically, the resistivity can be freely varied by varying theamount of CB powder to be mixed. The film of the invention may have, forexample, a resistivity within the range of VR: 10² to 10¹⁴ and SR: 10³to 10¹⁵, and preferably VR: 10⁶ to 10¹³ and SR: 10⁷ to 10¹⁴. Such aresistivity range can be easily achieved by using CB powder in an amountas specified above. The CB content of the film of the invention isusually about 5 to about 30% by weight, and preferably about 9 to about23% by weight.

The semi-conductive PI film of the present invention has extremelyuniform electrical resistivity. More specifically, the semi-conductivePI film of the invention is characterized by small variation in logsurface resistivity SR and log volume resistivity VR; that is, their logstandard deviations of all the measurement points of the film are each0.2 or less, and preferably 0.15 or less. The film of the invention isalso characterized in that the difference in surface resistivities (interms of log) between its front and rear surfaces is as small as 0.4 orless, and preferably 0.2 or less. The film of the invention is furthercharacterized in that the value obtained by subtracting Log VR (logvolume resistivity) from Log SR (log surface resistivity) can bemaintained at a level as high as 1.0 to 3.0, and preferably 1.5 to 3.0.

Such excellent electrical characteristics of the PI film of the presentinvention are attributed to the fact that, because ahigh-molecular-weight polyimide precursor or high-molecular-weightpolyamideimide solution has been mixed therein, CB is uniformlyphysically incorporated into the entangling structure of the polymerchains, and accordingly, the effects caused by evaporation of solventand/or the effects of polymerization of the nylon salt-type monomerduring film production are reduced, whereby a conductive seamlesspolyimide-based film can be obtained while maintaining the uniformdispersion of CB achieved in the precursor composition solution.

The PI film of the invention is applicable to a wide range of uses dueto its excellent electrical resistance properties and othercharacteristics. Examples of important applications that requireelectrostatic properties include electrophotographic intermediatetransfer belts for color printers, color copying machines, or the like.Such a belt requires a semiconductivity (resistivity) of, for example,VR 10⁹ to 10¹² and SR 10¹⁰ to 10¹³, and accordingly, the semi-conductiveseamless tubular PI-based film of the invention is suitable.

The semi-conductive PI film of the invention is highly efficient as abelt, and has high yield stress (σ_(Y)) and high tensile strength(σ_(cr)). The yield stress (σ_(Y)) is 120 Mpa or more, particularly 120to 160 Mpa, and the ratio of tensile strength to yield stress(σ_(cr)/σ_(Y)) is 1.10 or more, particularly about 1.10 to about 1.35.

D. FOURTH EMBODIMENT

The electrically semi-conductive seamless tubular polyimide film(hereinafter sometimes referred to as “semi-conductive tubular PI film”)of the present invention is produced by rotationally molding and heattreating (imidizing) a semi-conductive high-concentration polyimideprecursor composition (hereinafter sometimes referred to as“semi-conductive high-concentration PI precursor composition”).

D-1. Semi-Conductive High-Concentration Polyimide Precursor Composition

The semi-conductive high-concentration polyimide precursor compositionis produced by first uniformly dispersing carbon black (hereinaftersometimes refered to as “CB”) in an organic polar solvent to obtain acarbon black dispersion, and then dissolving approximately equimolaramounts of aromatic tetracarboxylic acid diester and aromatic diamine inthe carbon black dispersion. That is, the composition is characterizedin that it is produced by adding equimolar amounts of monomer startingmaterials (i.e., equimolar amounts of aromatic tetracarboxylic aciddiester and aromatic diamine) to a pre-prepared uniform CB dispersion.

(1) Carbon Black Dispersion

In the present invention, conductive CB powder is used to impartsemiconductivity to a PI precursor composition. The reason for using CBpowder is that (compared with other known conducting materials such asmetals and metal oxides) CB exhibits excellent dispersibility as well asexcellent stability (change over time after mixing and dispersion) in aprepared semi-conductive high-concentration polyimide precursorcomposition, and does not have any adverse effects on polycondensation.

There are various kinds of CB powder with various properties (electricalresistance, volatile content, specific surface area, particle diameter,pH value, DBP oil absorption, etc.) depending on the source (naturalgas, acetylene gas, coal tar, etc.) and production conditions(combustion conditions). It is desirable to employ CB powder that iscapable of stably providing a desired electrical resistance withoutvariation even when a minimum amount thereof is mixed and dispersed.

Such conductive CB powder usually has a mean particle diameter of about15 to about 65 nm. When used, for example, for electrophotographicintermediate transfer belts for color printers, color copying machinesor the like, CB powder having a mean particle diameter of about 20 toabout 40 nm is particularly preferable.

Carbon black having a high conductivity index, such as ketjen black andacetylene black, is likely to lead to the formation of secondaryaggregation (structure) and the occurrence of a conductivity chain, andaccordingly, control within a semi-conductive range is difficult.Therefore, use of acidic carbon black, which is unlikely to lead to suchstructure formation, is effective.

Examples thereof include channel black and oxidized furnace black.Specific examples include Special Black 4 (pH 3, volatile content 14%,particle diameter 25 nm) and Special Black 5 (pH 3, volatile content15%, particle diameter 20 nm), manufactured by Degusa Corporation.

An aprotic organic polar solvent is preferable as an organic polarsolvent used for a carbon black dispersion. Examples thereof includeN-methyl-2-pyrrolidone (hereafter referred to as “NMP”),N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide,dimethylsulfoxide, hexamethylphosphoramide, and1,3-dimethyl-2-imidazolidinone. Such solvents may be used singly, and amixed solvent of two or more such solvents can also be used. NMP isparticularly preferable.

A carbon black dispersion is produced by uniformly dispersing CB powderin such an organic polar solvent. The method for mixing CB powder is notlimited as long as such CB powder can be uniformly mixed and dispersedin an organic polar solvent. For example, ball mills, sand mills, andultrasonic mills are usable.

CB powder is used in an amount of about 3 to about 25 parts by weight,and preferably about 5 to about 15 parts by weight, per 100 parts byweight of organic polar solvent. These amounts are in a range where theviscosity of the organic polar solvent does not increase and secondaryaggregation of CB due to Van der Waals force is prevented. The lowerlimit is set at not less than 3 parts by weight per 100 parts by weightof organic polar solvent because at least such an amount is necessary inorder to prevent decrease in the nonvolatile content of a producedhigh-concentration polyimide precursor composition. The upper limit isset at not more than 25 parts by weight for the purpose of maintainingenough distance between the uniformly dispersed CB powder particles andthereby preventing secondary coagulation due to Van der Waals force.

(2) Aromatic Tetracarboxylic Acid Diesters (Half Esterified)

A mixture of at least one asymmetric aromatic tetracarboxylic aciddiester and at least one symmetric aromatic tetracarboxylic acid diesteris used as at least two aromatic tetracarboxylic acid diester startingmaterials.

Asymmetric aromatic tetracarboxylic acid diesters for use in the presentinvention are explained hereinafter.

Examples of asymmetric aromatic tetracarboxylic acids include:

compounds in which four carboxyl groups are boundnon-point-symmetrically to a monocyclic or polycyclic aromatic ringsystem (e.g., benzene nucleus, naphthalene nucleus, biphenyl nucleus,and anthracene nucleus); and

compounds in which four carboxyl groups are boundnon-point-symmetrically to two monocyclic aromatic rings (e.g., benzenenuclei) linked by a group such as —CO—, —CH₂— or —SO₂—, or by a singlebond.

Specific examples of asymmetric aromatic tetracarboxylic acids include1,2,3,4-benzenetetracarboxylic acid, 1,2,6,7-naphthalenetetracarboxylicacid, 2,3,3′,4′-biphenyltetracarboxylic acid,2,3,3′,4′-benzophenonetetracarboxylic acid, 2,3,3′,4′-diphenyl ethertetracarboxylic acid, 2,3,3′,4′-diphenylmethanetetracarboxylic acid, and2,3,3′,4′-diphenylsulfonetetracarboxylic acid.

Examples of asymmetric aromatic tetracarboxylic acid diesters (i.e.,half esterified) for use in the present invention include diesters ofsuch asymmetric aromatic tetracarboxylic acids. Specific examplesthereof include compounds in which two of the four carboxyl groups ofthe asymmetric aromatic tetracarboxylic acid are esterified with one ofeach pair of adjacent carboxyl groups on an aromatic ring beingesterified.

Examples of the two esters of such asymmetric aromatic tetracarboxylicacid diesters include di(lower alkyl)esters, and preferably C₁₋₃ alkylesters, such as dimethyl esters, diethyl esters, and dipropyl esters(particularly, dimethyl esters).

Among such asymmetric aromatic tetracarboxylic acid diesters,2,3,3′,4′-biphenyltetracarboxylic acid dimethyl esters and2,3,3′,4′-biphenyltetracarboxylic acid diethyl esters are preferable,with 2,3,3′,4′-biphenyltetracarboxylic acid dimethyl esters beingparticularly preferable.

Asymmetric aromatic tetracarboxylic acid diesters as above arecommercially available, and can also be produced by known methods. Theycan be easily produced, for example, by reacting the correspondingasymmetric aromatic tetracarboxylic dianhydride with the correspondingalcohol (e.g., lower alcohol, preferably C₁₋₃ alcohol) at a molar ratioof 1:2. By such a method, the acid anhydride, which is a startingmaterial, reacts with the alcohol and thereby undergoes ring opening,providing a diester (half esterified) having an ester group and acarboxyl group on respective adjacent carbons on an aromatic ring.

Symmetric aromatic tetracarboxylic acid diesters for use in the presentinvention are explained hereinafter.

Examples of symmetric aromatic tetracarboxylic acids include:

compounds in which four carboxyl groups are bound point-symmetrically toa monocyclic or polycyclic aromatic ring system (e.g., benzene nucleus,naphthalene nucleus, biphenyl nucleus, and anthracene nucleus); and

compounds in which four carboxyl groups are bound point-symmetrically totwo monocyclic aromatic rings (e.g., benzene nuclei) linked by a groupsuch as —CO—, —O—, —CH₂— or —SO₂—, or by a single bond.

Specific examples of symmetric aromatic tetracarboxylic acids include1,2,4,5-benzenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylicacid, 3,3′,4,4′-biphenyltetracarboxylic acid, 3,3′,4,4′-benzophenonetetracarboxylic acid, 3,3′,4,4′-diphenyl ether tetracarboxylic acid,3,3′,4,4′-diphenylmethanetetracarboxylic acid, and3,3′,4,4′-diphenylsulfonetetracarboxylic acid.

Examples of symmetric aromatic tetracarboxylic acid diesters (i.e., halfesterified) for use in the present invention include diesters of suchsymmetric aromatic tetracarboxylic acids (i.e., half esterified).Specific examples thereof include compounds in which two of the fourcarboxyl groups of the symmetric aromatic tetracarboxylic acid areesterified with one of each pair of adjacent carboxyl groups on anaromatic ring being esterified.

Examples of the two esters of such symmetric aromatic tetracarboxylicacid diesters include di(lower alkyl)esters, and preferably C₁₋₃ alkylesters, such as dimethyl esters, diethyl esters, and dipropyl esters(particularly, dimethyl esters).

Among such symmetric aromatic tetracarboxylic acid diesters,3,3′,4,4′-biphenyltetracarboxylic acid dimethyl esters,3,3′,4,4′-biphenyltetracarboxylic acid diethyl esters,1,2,4,5-benzenetetracarboxylic acid dimethyl esters, and1,2,4,5-benzenetetracarboxylic acid diethyl esters are preferable, with3,3′,4,4′-biphenyltetracarboxylic acid dimethyl esters beingparticularly preferable.

Symmetric aromatic tetracarboxylic acid diesters as above arecommercially available, and can also be produced by known methods. Theycan be easily produced, for example, by a known method of reacting thecorresponding symmetric aromatic tetracarboxylic dianhydride with thecorresponding alcohol (e.g., lower alcohol, preferably C₁₋₃ alcohol) ata molar ratio of 1:2. By such a method, the acid anhydride, which is astarting material, reacts with the alcohol and thereby undergoes ringopening, providing a diester (half esterified) having an ester group anda carboxyl group on respective adjacent carbons on an aromatic ring.

The mixing ratio for asymmetric and symmetric aromatic tetracarboxylicacid diesters is specified such that the proportion of asymmetricaromatic tetracarboxylic acid diester(s) is about 10 to about 50 mol %(and preferably about 20 to about 40 mol %) and the proportion ofsymmetric aromatic tetracarboxylic acid diester(s) is about 90 to about50 mol % (and preferably about 80 to about 60 mol %). It is particularlypreferable to use about 20 to about 30 mol % of asymmetrictetracarboxylic aromatic acid diester(s) and about 70 to about 80 mol %of symmetric aromatic tetracarboxylic acid diester(s).

The combined use of such symmetric and asymmetric aromatictetracarboxylic acid diesters is essential for the following reasons.Use of only symmetric aromatic tetracarboxylic acid diesters inducescrystallization of a polyimide film and thereby causes powderization ofthe film during heat treatment, which thus cannot achieve filmformation. Although use of only asymmetric aromatic tetracarboxylic acidderivatives achieves the formation of a seamless tubular PI film, suchan obtained film has inferior yield stress and elastic modulus, and,when used as a rotational belt, it suffers from problems such as lowdriving responsiveness and early elongation of the belt.

In contrast, the use of mixed aromatic tetracarboxylic acid diestersachieves extremely high film-forming capability (formability), andprovides a semi-conductive seamless tubular PI film having high yieldstress and elastic modulus.

Further, the addition of an asymmetric aromatic tetracarboxylic aciddiester presumably causes a polyamic acid molecule to bend, therebyimparting flexibility.

The effects of the coexistence of such asymmetric and symmetric aromatictetracarboxylic acid diesters are most apparent when they are mixed at aratio as specified above.

(3) Aromatic Diamine

Examples of aromatic diamines include compounds having two amino groupson a single aromatic ring (e.g., benzene nucleus), and compounds havingtwo amino groups in which two or more aromatic rings (e.g., benzenenuclei) are linked by a group such as —O—, —S—, —CO—, —CH₂—, —SO— or—SO₂—, or by a single bond. Specific examples thereof includep-phenylenediamine, o-phenylenediamine, m-phenylenediamine,4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl thioether,4,4′-diaminodiphenylcarbonyl, 4,4′-diaminodiphenylmethane, and1,4-bis(4-aminophenoxy)benzene. Among these, 4,4′-diaminodiphenyl etheris particularly preferable. Use of such an aromatic diamine allows thereaction to proceed more smoothly, and provides a film having greatertoughness and higher heat resistance.

(4) Semi-Conductive High-concentration Polyimide Precursor Composition

At least two aromatic tetracarboxylic acid diesters and an approximatelyequimolar amount of at least one aromatic diamine are added to aprepared carbon black dispersion, and dissolved therein.

Approximately equimolar amounts of aromatic tetracarboxylic acidcomponent and organic diamine component are added to a carbon blackdispersion, stirred, and uniformly dissolved therein, providing asemi-conductive high-concentration polyimide precursor composition.Heating may be performed (at, for example, about 40 to about 70° C.), ifnecessary, for such uniform dissolution of the components in a carbonblack dispersion. Stirring or like known method can be employed todissolve the components in the organic polar solvent therein.

The aromatic tetracarboxylic acid diesters and aromatic diamine are usedin an amount such that the proportion of carbon black in the carbonblack dispersion is about 5 to about 35 parts by weight (and preferablyabout 8 to about 30 parts by weight) per 100 parts by weight of thetotal amount of the aromatic tetracarboxylic acid diesters and thearomatic diamine(s). The purpose of using the components in such anamount is to provide the film with volume resistivity (VR) and surfaceresistivity (SR) in a semi-conductive range.

Such a semi-conductive high-concentration polyimide precursorcomposition presumably has a constitution in which, for example, ionpairs of carboxylate ions of the aromatic tetracarboxylic acid diestersand ammonium ions of the aromatic diamine are present in a substantiallymonomeric state in an organic polar solvent (see, e.g., the formulagiven below).

(Ar is a tetravalent residue obtained by removing two carboxyl groupsand two ester groups from an aromatic tetracarboxylic acid, Ar′ is adivalent residue obtained by removing two amino groups from an aromaticdiamine, and R is an alkyl group)

Such ions can be dissolved in an organic polymer solvent as aboveextremely easily because of their substantially monomeric state, thusproviding the advantage that the amount of solvent used can beminimized.

The composition may have a high nonvolative content of, for example,about 35 to about 60% by weight, and preferably about 40 to about 60% byweight. This nonvolatile matter may have a CB content of, for example,about 4 to about 30% by weight, and preferably about 10 to about 25% byweight. “Nonvolatile content” as used herein means a content measured bythe method described in Example D-1.

Additives such as imidazole compounds (e.g., 2-methylimidazole,1,2-dimethylimidazole, 2-methyl-4-methylimidazole,2-ethyl-4-ethylimidazole, and 2-phenylimidazole) and surfactants (e.g.,fluorosurfactants) can be added to the composition, within ranges thatthe effects of the present invention are not adversely affected.

A semi-conductive PI precursor composition is thereby produced, in whichCB powder is uniformly dispersed and nonvolatile matter is dissolved ordispersed at a high concentration.

Because the semi-conductive high-concentration PI precursor compositionof the present invention is obtained by dissolving aromatictetracarboxylic acid diesters and an aromatic diamine component in acarbon black dispersion prepared by uniformly dispersing CB powder, thecomposition has CB powder uniformly dispersed therein, and the storagestability of the uniform dispersion of the carbon black is remarkablyimproved. Further, a conductive polyimide tube formed by rotationallymolding such a semi-conductive PI precursor composition has excellentconductivity, i.e., extremely stable and uniform electrical resistivityin the thickness direction.

Because monomer starting materials are dissolved in a carbon blackdispersion, the semi-conductive high-concentration PI precursorcomposition of the present invention has a remarkably increasednonvolatile content of about 35 to about 60% by weight. Accordingly,using the semi-conductive high-concentration PI precursor composition ofthe present invention, a thick film can be readily produced, and,because only a small amount of solvent is required, costs can be reducedand the evaporative removal of solvent can be simplified.

Further, the semi-conductive high-concentration PI precursor compositionof the invention has an increased viscosity of about 10 to about 60poise, and accordingly, in the production of a PI film, effects ofcentrifugal force during rotational molding are reduced.

D-2. Semi-Conductive Seamless Tubular Polyimide Film

Hereinafter, a process of forming a semi-conductive seamless tubular PIfilm using a semi-conductive PI precursor composition as prepared aboveis described.

Rotational molding using a rotating drum is employed for this formationprocess. First, a semi-conductive PI precursor composition is introducedinto a rotating drum and uniformly cast over the entire inner surface.

The method for introduction/casting may be such that, for example, asemi-conductive PI precursor composition in an amount sufficient toprovide the desired final film thickness is introduced into a rotatingdrum while stationary, and the rotational speed is then gradually raisedto an extent that centrifugal force is generated. The composition iscast uniformly over the entire inner surface by the centrifugal force.Alternatively, introduction/casting may be performed without usingcentrifugal force. According to one possible method, a horizontallyelongated slit-like nozzle is arranged inside a rotating drum, and,while slowly rotating the drum, the nozzle is rotated (at a speedgreater than the drum rotational speed). The film-formationsemi-conductive PI precursor composition is uniformly ejected from thenozzle over the entire inner surface of the drum. The drum is mounted onrotating rollers, and is rotated indirectly by the rotation of therollers.

A far-infrared radiation heater or like heat source is arranged aroundthe drum, and heating is carried out indirectly by such an external heatsource. The size of the drum depends on the size of the desiredsemi-conductive tubular PI film.

Heating is first carried out so that the inner surface of the drum isgradually heated to about 100 to about 190° C., and preferably to about110 to about 130° C. (first heating step). The rate of heating is about1 to about 2° C./min. This temperature is maintained for 1 to 3 hours,so that approximately half or more of the solvent is volatized, and aself-supporting tubular film is thereby formed. Although imidizationrequires a temperature of 280° C. or higher, if heating is carried outat such a high temperature from the beginning, the polyimide becomeshighly crystalline, which adversely affects the CB dispersion state,further causing problems such as a film thus formed lacking toughness.Therefore, as a first heating step, the temperature is raised not higherthan about 190° C., and the polycondensation reaction is completed atsuch a temperature, so as to obtain a tough tubular PI film.

After this step, heating to complete imidization is then carried out asa second heating step at about 280 to about 400° C. (and preferablyabout 300 to about 380° C.). In this step, the temperature is alsopreferably raised from the temperature of the first heating stepgradually, rather than rapidly.

The second heating step may be performed while the seamless tubular filmis adhered to the inner surface of the rotating drum, or alternatively,it is also possible to separate and remove the seamless tubular filmfrom the rotating drum after the first heating step, and separately heatthe film to 280 to 400° C. by a heating means for imidization. Suchimidization usually takes about 2 to 3 hours. Accordingly, the entireprocess of the first and second heating steps usually takes about 4 toabout 7 hours in total.

A semi-conductive tubular PI film of the invention is thus produced. Thefilm usually has a thickness of about 30 to about 200 μm, although notlimited thereto, and preferably about 60 to about 120 μm. When used asan electrophotographic intermediate transfer belt, a thickness of about75 to about 100 μm is particularly preferable.

The semiconductivity of the film is an electrical resistance propertydetermined by the volume resistivity (Ω·cm) (hereinafter referred to as“VR”) and surface resistivity (Ω/sq) (hereinafter referred to as “SR”).Such a property is due to CB powder having been mixed and dispersedtherein. Basically, the resistivity can be freely varied by varying theamount of CB powder to be mixed. The film of the invention may have, forexample, a resistivity within the range of VR: 10² to 10¹⁴ and SR: 10³to 10¹⁵, and preferably VR: 10⁶ to 10¹³ and SR: 10⁷ to 10¹⁴. Such aresistivity range can be easily achieved by using CB powder in an amountas specified above. The CB content of the film of the invention isusually about 5 to about 25% by weight, and preferably about 8 to about20% by weight.

The semi-conductive tubular PI film of the invention has extremelyuniform electrical resistivity. More specifically, the semi-conductivetubular PI film of the invention is characterized by small variation inlog surface resistivity SR and log volume resistivity VR; that is, thierlog standard deviations of all the measurement points of the film areeach 0.2 or less, and preferably 0.15 or less. The film of the inventionis also characterized in that the difference in surface resistivities(in terms of log) between its front and rear surfaces is as small as 0.4or less, and preferably 0.2 or less. The film of the invention isfurther characterized in that the value obtained by subtracting Log VR(log volume resistivity) from Log SR (log surface resistivity) can bemaintained at a level as high as 1.0 to 3.0, and preferably 1.5 to 3.0.

The PI film of the invention is applicable to a wide range of uses dueto its excellent electrical resistance properties and othercharacteristics. Examples of important applications that requireelectrostatic properties include electrophotographic intermediatetransfer belts for color printers, color copying machines, or the like.Such a belt requires a semiconductivity (resistivity) of, for example,VR 10⁹ to 10¹² and SR 10¹⁰ to 10¹³, and accordingly, the semi-conductiveseamless tubular PI film of the invention is suitable.

The semi-conductive PI film of the invention is highly efficient as abelt, and has high yield stress (σ_(Y)) and high tensile strength(σ_(cr)). The yield stress (σ_(Y)) is 120 Mpa or more, particularly 120to 160 Mpa, and the ratio of tensile strength to yield stress(σ_(cr)/σ_(Y)) is 1.10 or more, particularly about 1.10 to about 1.35.

BEST MODE OF CARRYING OUT THE INVENTION

The present invention will be described below in greater detail withreference to Examples and Comparative Examples. The invention, however,is not limited to these examples.

A. FIRST EMBODIMENT

The first embodiment will be described below in much greater detail withreference to Examples and Comparative Examples.

In this example, yield stress (yield point stress), tensile strength,volume resistivity (VR), surface resistivity (SR), and nonvolatilematter content are measured as follows. [yield stress (MPa) (referred toas σ_(y)) and tensile strength (MPa) (referred to as σ_(cr))]

A test piece 5 mm wide and 100 mm long was cut from a film as preparedin one of each of the Examples described below, and was measured by auniaxial tensile tester (Autograph, a product of Shimadzu) at a gaugelength of 40 mm and a crosshead of 200 mm/min. Based on the S—S curverecorded, σ_(Y) and σ_(cr) were determined.

These yield stress and tensile strength values are important factors indetermining the strength of a material for a belt in preparing the same.The required minimum yield stress is at least 120 MPa so as to preventplastic deformation (dimensional change by elongation) caused by stressapplied during mounting.

Moreover, the tensile strength needs to be higher than the yield stress,which contributes to the life (toughness) against rotations of the belt.As a guide, at least σ_(cr)/σ_(Y)=1.10 is required.

[VR and SR]

A sample 400 mm long was cut from the obtained tubular film and wasmeasured using a resistivity meter, “Hiresta IP/HR probe”, manufacturedby Mitsubishi Chemical Corporation at 40 points in total: five points inthe width direction and eight points in the vertical direction(circumference) at the same pitch.

Note that VR was measured while applying a voltage of 100 V, 10 secondsafter beginning to apply the voltage and SR was measured while applyinga voltage of 500 V, 10 seconds after beginning to apply the voltage.

[Nonvolatile Matter Content]

A sample (monomer mixed solution, etc.) was precisely weighed using aheat-resistant container, such as a metal cup, etc., and the preciselymeasured weight of the sample was defined as “A” g. The heat-resistantcontainer containing the sample was placed in an electric oven, and thenheated and dried while raising the temperature of the oven gradually:120° C. for 12 minutes, 180° C. for 12 minutes, 260° C. for 30 minutes,and 300° C. for 30 minutes. The solid matter weight (nonvolatile matterweight) thus determined was defined as “B” g. Five A values and five Bvalues obtained from the same sample were measured (n=5), and applied tothe following formula (I) to determine the nonvolatile matter content.The average of the values obtained from the five samples was defined asthe nonvolatile matter content in the invention.Nonvolatile matter content=B/A×100(%)  (I)

EXAMPLE A-1

716.0 g (2.0 mol) of 2,3,3′,4′-biphenyltetracarboxylic acid dimethylester (half esterified product formed by the reaction of 2 mol of methylalcohol per mol of 2,3,3′,4′-biphenyltetracarboxylic dianhydride) and400.0 g (2.0 mol) of 4,4′-diaminodiphenyl ether were mixed at roomtemperature in 1540 g of NMP solvent. The mixture was dissolveduniformly to form a solution. This solution had a nonvolatile mattercontent of 34.6% by weight and a solution viscosity of about 250 mPa·s.The solution substantially did not undergo polycondensation andtherefore was stable in a monomeric state. Hereinafter, this solution isreferred to as “asymmetric monomer solution A”.

716.0 g (2.0 mol) of 3,3′,4,4′-biphenyl tetracarboxylic acid dimethylester (half esterified product formed by the reaction of 2 mol of methylalcohol per mol of 3,3′,4,4′-biphenyltetracarboxylic dianhydride) and400.0 g (2.0 mol) of 4,4′-diaminodiphenyl ether were mixed at roomtemperature in 1540 g of NMP solvent. The mixture was uniformlydissolved to form a solution. This solution had a nonvolatile mattercontent of 34.6% by weight and a solution viscosity of about 250 mPas.The solution substantially did not undergo polycondensation andtherefore was stable in a monomeric state. Hereinafter, this solution isreferred to as “symmetric monomer solution B”.

The asymmetric monomer solution A and the symmetric monomer solution Bwere mixed thoroughly in the proportions shown in the rows of Ex. 1 andEx. 2 of Table A-1 with 0.037% by weight (based on the nonvolatilematter content) of fluorosurfactant (EF-351, a product of TohkemProducts), followed by degassing, giving a monomer solution C. Apredetermined amount of the solution was weighed out from the monomersolution C. Each solution was injected into a rotating drum; and filmswere formed under the following conditions.

Rotating drum: A metal drum with a mirror-finished inner surface havingan inner diameter of 100 mm and a width of 530 mm was placed on tworotating rollers in such a manner as to rotate with the rotation of therollers.

Injection amount of film-formation monomer solution C: 45.9 g

Heating temperature: A far-infrared heater was placed on the outersurface of the drum, so that the temperature of the inner surface of thedrum was adjusted to be 170° C.

45.9 g of each monomer solution was uniformly injected into the bottomof the rotating drum in a non-rotating state.

Immediately thereafter, rotation of the drum was started, and therotation rate was gradually increased to 24 rad/s. Subsequently, thesolution was uniformly applied over the entire inner surface of the drumby pouring it thereon, followed by heating. The heating temperature wasincreased gradually to 170° C., at which the drum was further heated for90 minutes while continuously rotating.

After the 90-minute heating and rotation was complete, the drum wascooled to room temperature. The rotating drum was then taken off, andleft to stand in a hot air circulating oven to be heated forimidization. The content was heated while gradually raising the heatingtemperature to 350° C., at which the content was further heated for 30minutes, followed by cooling to room temperature. The tubular PI filmformed on the inner surface of the drum was peeled off and removed. Themeasurement results obtained in each Example are shown in Table A-2.TABLE A-1 Mol % of asymmetric Weight ratio of asymmetric monomersolution A and CB powder amount, monomer solution A and symmetricmonomer per 100 parts by weight of Ex. symmetric monomer solution Bsolution B starting material monomer No. Solution A Solution B SolutionA Solution B (parts by weight) Ex. A-1 1 200 200 50 50 0 2 80 320 20 800 Com. 3 280 120 70 30 0 Ex. A-1 4 40 360 10 90 0 5 0 200 0 100 0 6 2000 100 0 0 Ex. A-2 7 200 200 50 50 8.33 Com. 8 280 120 70 30 8.33 Ex. A-29 40 360 10 90 8.33

TABLE A-2 Film Yield Tensile Ex. Thickness stress strength VR No (μm)σ_(Y) (MPa) σ_(cr) (MPa) σ_(cr)/σ_(Y) (Ω · cm) SR (Ω/sq) Note Ex. A-1 185 132.5 147 1.11 2.8 × 10¹⁴ 1.0 × 10¹⁶ Com. 2 85 145 172.5 1.19 Same asSame as Ex. A-1 above above 3 85 123.5 123.5 1 Same as Same as aboveabove 4 — — — — — — fragile and unmeasurable 5 — — — — — — fragile andunmeasurable 6 85 116 117.5 0.99 2.8 × 10¹⁴ 1.0 × 10¹⁶ Ex. A-2 7 85 131144.5 1.1 3.0 × 10¹⁰ 1.4 × 10¹² Com. 8 85 119.5 120 1 4.2 × 10¹⁰ 5.0 ×10¹² Ex. A-2 9 — — — — — — fragile and unmeasurable

COMPARATIVE EXAMPLE A-1

The same procedure as in Example A-1 was performed except that thesymmetric monomer solution A and the symmetric monomer solution B asprepared in Example A-1 were mixed in the proportions shown in the rowsof Exs. 3 to 6 of Table A-1. The results weight each example are shownin Table A-2.

EXAMPLE A-2

The asymmetric monomer solution A and the symmetric monomer solution Bas prepared in Example A-1 were uniformly mixed in the proportions shownin the row of Ex. 7 of Table A-1 in the same manner as in Example A-1.Thereafter, 14.0 g (8.33 parts by weight per 100 parts by weight of thetotal amount of all the monomers) of CB powder (pH 3, particle diameterof 23 run) was added to the solution. The mixture was thoroughly mixedand dispersed using a ball mill, and finally degassed, yielding afilm-formation semi-conductive monomer solution. The film-formationsemi-conductive monomer solution had a nonvolatile matter content of36.8% by weight and a CB content in the nonvolatile matter of 9.19% byweight.

45.9 g of the solution was weighed out, and poured into a rotating drumin the same manner as in Example A-1. The result was formed and imidizedunder the same conditions as in Example A-1. The imidized film waspeeled off and removed for measurement. The measurement results of thesample are shown in Table A-2.

COMPARATIVE EXAMPLE A-2

The asymmetric monomer solution A and the symmetric monomer solution Bas prepared in Example A-1 were uniformly mixed in the proportions shownin the rows of Exs. 8 and 9 of Table A-1 in the same manner as inExample A-1. Thereafter, CB powder was added to each solution in anamount of 8.33 parts by weight, per 100 parts by weight of the totalamount of all the monomers in the same manner as in Example A-2. Eachmixture was thoroughly mixed and dispersed using a ball mill, andfinally degassed, yielding a film-formation semi-conductive monomersolution. Each film-formation semi-conductive monomer solution had anonvolatile matter content of 36.8% by weight and a CB content in thenonvolatile matter of 9.19% by weight.

45.9 g of each solution was weighed out, and poured in a rotating drumin the same manner as in Example A-1. The results were formed andimidized under the same conditions as in Example A-1. The imidized filmswere peeled off and removed for measurement. The measurement results ofeach film are shown in Table A-2.

B. SECOND EMBODIMENT

The second embodiment will be described below in much greater detailwith reference to examples and comparative

EXAMPLE B-1

358.0 g (1.0 mol) of 2,3,3′,4′-biphenyltetracarboxylic acid dimethylester (diester product formed by the reaction of 2 mol of methyl alcoholper mol of 2,3,3′,4′-biphenyltetracarboxylic dianhydride), 358.0 g (1.0mol) of 3,3′,4,4′-biphenyl tetracarboxylic acid dimethyl ester (diesterproduct formed by the reaction of 2 mol of methyl alcohol per mol of3,3′,4,4′-biphenyltetracarboxylic dianhydride), and 400 g (2 mol) of4,4′-diaminodiphenylether were mixed and uniformly dissolved in 1674 gof NMP solvent at 60° C. to form a solution. Subsequently, the solutionwas heated while raising the temperature to 100° C. over one hour, atwhich the solution was further heated for one hour, followed by cooling.This solution was in the oligomeric state and had a nonvolatile mattercontent of 32.9% by weight and a number average molecular weight of2000, and is referred to as “oligomer mixed solution A”.

To 1000 g of the oligomer mixed solution A were added 71.7 g of carbonblack (CB) powder (pH 3, particle diameter 23 nm) and 142.5 g of NMP.The mixture was thoroughly mixed and dispersed using a ball mill andfinally degassed, giving a film-formation semi-conductive oligomersolution. This semi-conductive oligomer solution had a nonvolatilematter content of 33.0% by weight and a CB content in the nonvolatilematter of 17.89% by weight.

109 g of the solution was weighed out, poured in a rotating drum; andformed under the following conditions.

Rotating drum: A metal drum with a mirror-finished inner surface havingan inner diameter of 175 mm and a width of 540 mm was placed on tworotating rollers in such a manner as to rotate with the rotation of therollers.

Heating temperature: A far-infrared heater was placed on the outersurface of the drum, so that the temperature of the inner surface ofthis drum was adjusted to be 120° C.

109 g of the solution was uniformly applied to the inner surface of thedrum as it was rotating, and then heated. The heating temperature wasgradually raised by 2° C./min to reach 120° C. The rotating drum wasthen heated at 120° C. for 90 minutes while continuously rotating.

After the rotation and heating was complete, the drum was not cooled butremoved. The drum was then left to stand in a hot air-circulating ovento be heated for imidization. The drum was heated while graduallyraising the heating temperature to 320° C., at which the content wasfurther heated for 30 minutes, followed by cooling to room temperature.Subsequently, the semi-conductive tubular PI film formed on the innersurface of the drum was peeled off and removed. The thickness of thefilm was 90 μm.

The “nonvolatile matter content” in the specification was calculated asfollows. A sample (semi-conductive oligomer solution, etc.) wasprecisely weighed using a heat-resistant container, such as a metal cup,etc., and the precisely-measured weight of the sample was defined as “A”g. The heat-resistant container containing the sample was placed in anelectric oven, and then heated and dried while raising the temperaturegradually: 120° C. for 12 minutes, 180° C. for 12 minutes, 260° C. for30 minutes, and 300° C. for 30 minutes. The solid matter weight(nonvolatile matter weight) thus determined was defined as “B” g. Five Avalues and five B values obtained from the same sample were measured(n=5), and applied to the following formula (I) to determine thenonvolatile matter content. The average of the values obtained from thefive samples was defined as the nonvolatile matter content in theinvention.Nonvolatile matter content=B/A×100(%)  (I)

REFERENCE EXAMPLE B-1

Carboxylic acid dimethyl ester and diaminodiphenyl ether were mixed inthe same proportions as in Example B-1, and the mixture was dissolved at60° C. to form a solution. The solution was cooled. This solution had anonvolatile matter content of 32.9% by weight and was substantially in amonomeric state, and is referred to as “monomer mixed solution A”.

To 1000 g of the monomer mixed solution A were added 31.0 g of CB powder(pH 3, particle diameter 23 nm) and 60.0 g of NMP. The mixture wasthoroughly mixed and dispersed using a ball mill and finally degassed,giving a film-formation semi-conductive monomer solution. Thissemi-conductive monomer solution had a nonvolatile matter content of33.0% by weight and a CB content in the nonvolatile matter of 8.61% byweight.

109 g of the solution was weighed out. Then, in the same manner as inExample B-1, the solution was heated and formed, giving asemi-conductive tubular PI film, and the film was peeled off andremoved. The thickness of the film was 92 μm.

EXAMPLE B-2

143.2 g (0.4 mol) of 2,3,3′,4′-biphenyltetracarboxylic acid dimethylester (diester product formed by the reaction of 2 mol of methyl alcoholper 1 mol of 2,3,3′,4′-biphenyltetracarboxylic dianhydride), 572.8 g(1.6 mol) of 3,3′,4,4′-biphenyl tetracarboxylic acid dimethyl ester(diester product formed by the reaction of 2 mol of methyl alcohol permol of 3,3′,4,4′-biphenyltetracarboxylic dianhydride), and 400 g (2 mol)of 4,4′-diaminodiphenylether were mixed and dissolved uniformly in 1674g of NMP solvent at 60° C. to form a solution. Subsequently, thesolution was heated while raising the temperature to 110° C. over onehour, at which the solution was further heated for one hour, followed bycooling. This solution was in the oligomeric state and had a nonvolatilematter content of 32.9% by weight and a number average molecular weightof 4000, and is referred to as “oligomer mixed solution B”.

To 1000 g of the oligomer mixed solution B were added 78.9 g of CBpowder (pH 3, particle diameter 23 nm) and 157.1 g of NMP. The mixturewas thoroughly mixed and dispersed using a ball mill and finallydegassed, giving a film-formation semi-conductive oligomer solution.This semi-conductive oligomer solution had a nonvolatile matter contentof 33.0% by weight and a CB content in the nonvolatile matter of 19.34%by weight.

109 g of the solution was weighed out, and poured in a rotating drum. Inthe same manner as in Example B-1, the solution was heated and formed,giving a semi-conductive tubular PI film, and the film was peeled offand removed. The thickness of the film was 89 μm.

COMPARATIVE EXAMPLE B-1

Carboxylic acid dimethyl ester and diaminodiphenyl ether were mixed inthe same proportions as in Example B-1, and the mixture was dissolved byheating at 60° C., to form a solution. Subsequently, the solution washeated while raising the temperature to 130° C. over one hour, at whichthe solution was further heated for one hour, followed by cooling. Aftercooling, the solution became turbid and formed a gel-like solid, andthus was not used for film formation.

The gel was not re-dissolved even when diluted in a solvent. Themeasurement of imidization proportion of the gel formed showed thatapproximately 35% imidization proceeded. This is presumably because theheating temperature was too high and therefore imidization excessivelyproceeded, which lowered the solubility and thus the resin content wasprecipitated.

TEST EXAMPLE B-1

The film formation conditions of Examples B-1, B-2, Reference ExampleB-1, and Comparative Example B-1, and the measured electricalresistivities of the films obtained are shown in Table B-1. Table B-1shows the average and standard deviations of surface resistivities andvolume resistivities in terms of log.

[Number Average Molecular Weight]

The number average molecular weight was determined by GPC (solvent: NMP,calculated with reference to polyethylene oxide).

[Imidization Proportion]

The imidization proportion was determined using an infrared spectroscopybased on an intensity ratio of imide absorption (1780 cm⁻¹) and benzenering absorption (1510 cm⁻¹). The benzene ring absorption was used as acontrol because it did not change in an imide precursor or imidizedproduct.

[Measurement of Surface Resistivity (SR) and Volume Resistivity (VR)]

A sample 400 mm long was cut from the obtained tubular film and wasmeasured using a resistivity meter, “Hiresta IP/HR probe” manufacturedby Mitsubishi Chemical Corporation at 12 points in total: three pointsin the width direction and four points in the vertical direction(circumference) at the same pitch. The average values were thenobtained.

Note that the volume resistivity VR was measured while applying avoltage of 100 V, 10 seconds after beginning to apply the voltage and SRwas measured while applying a voltage of 500 V, 10 seconds afterbeginning to apply the voltage. TABLE B-1 Number Ratio of asymmetricHeating average component to symmetric CB powder Film temper- molecularImidization component content thickness ature weight proportionAsymmetric Symmetric in a film Av. Ex. B-2 100° C. 2000 10% 50 50 17.8990 μm Ex. B-2 110° C. 4000 20% 20 80 19.34 89 μm Ref.  60° C.  250  0%50 50 8.61 92 μm Ex. B-1 Com. 130° C. 35% 50 50 Ex. B-1 Surfaceresistivity Surface of the resistivity film-front of the Volume surfacefilm-rear resistivity Difference in surface (log SR) surface (log VR)resistivities Standard Standard Standard between front logSR- Av.deviation Av. deviation Av. deviation and rear surfaces log VR Ex. B-211.77 0.11 11.87 0.09 9.88 0.11 0.10 1.89 Ex. B-2 11.93 0.11 12.07 0.1310.49 0.08 0.14 1.44 Ref. 11.99 0.30 12.40 0.25 12.10 0.43 0.41 −0.11Ex. B-1 Com. Ex. B-1Note:Average and standard deviations of surface resistivities and volumeresistivities in terms of logMeasurement of resistivity: 3 points in the belt-width direction × 4points in the circumferential direction = 12 points in totalVoltage application: while applying a voltage of 100 V, 10 seconds afterbeginning to apply the voltageResistivity meter: Hiresta IP/HR probe

Table B-1 shows that the standard deviations of the surfaceresistivities and the volume resistivities of the films of the Examplesare very small, i.e., less variation, compared with those the films ofReference Examples and Comparative Examples.

Moreover, the differences in surface resistivities (in terms of log)between the front and rear surfaces of the films of Examples areextremely small, and thus are preferable as intermediate transfer beltsfor use in color copiers.

Furthermore, in general, an increase in the heating temperatureelevation rate during film formation lowers the value (Log (SR/VR))obtained by subtracting volume resistivity in terms of log (LogVR) fromthe surface resistivity in terms of log (LogSR). Therefore, the use of afilm with such characteristic for a transfer belt results in failure ofappropriate electrically charging and/or electrically discharging, whichleads to poor image quality. It was however confirmed that this value ismaintained as high as 1.0-3.0 by the use of an oligomer mixed solution,thereby further increasing film productivity.

C. THIRD EMBODIMENT

The third embodiment will be described in much greater detail withreference to Examples and Comparative Examples. Hereinafter,2,3,3′,4′-biphenyltetracarboxylic dianhydride is referred to as “a-BPDA”and 3,3′,4,4′-biphenyl tetracarboxylic dianhydride is referred to as“s-BPDA”. The number average molecular weight was measured by GPC(solvent: NMP).

EXAMPLE C-1

22.8 g of methanol and 160 g of N-methyl-2-pyrrolidone were added to 14g (20 mol %) of a-BPDA and 56 g (80 mol %) of s-BPDA to react at a bathtemperature of 70° C. under a nitrogen stream. After cooling the bathtemperature to 65° C., 47.6 g of 4,4′-diaminodiphenyl ether (ODA) wasadded, followed by gentle stirring, giving 300.4 g of nylon salt monomersolution. This solution had a viscosity of 1.8 poise and a nonvolatilematter content of 36.3% by weight.

Separately, 47.6 g of ODA was added to 488 g of N-methyl-2-pyrolidoneunder a nitrogen stream. The mixture was kept warm at 50° C., and thencompletely dissolved by stirring. A powder comprising a mixture of 35 gof a-BPDA and 35 g of s-BPDA was gradually added to this solution,giving 605.6 g of a polyamic acid solution. This polyamic acid solutionhad a number average molecular weight of 16000, viscosity of 30 poise,and nonvolatile matter content of 18.0% by weight.

100 g of the nylon salt monomer solution and 80 g of the polyamic acidsolution were mixed, giving 180 g of a polyimide-based precursorsolution having a viscosity of 13 poise and nonvolatile matter contentof 28.2% by weight.

7.5 g of acidic carbon black (pH 3.0) and 16.7 g ofN-methyl-2-pyrrolidone were added to 150 g of this precursor solution touniformly disperse the carbon black using a ball mill. This masterbatchsolution had a nonvolatile matter content of 28.6% by weight; CB contentin the nonvolatile matter of 15.1% by weight; mean particle diameter ofcarbon black of 0.28 μm; and maximum particle diameter of carbon blackof 0.58 μm. Ten days later, the mean particle diameter and maximumparticle diameter of the carbon black hardly changed, and were 0.28 μmand 0.76 μm, respectively.

The “nonvolatile matter content” in the specification was calculated asfollows. A sample (nylon salt monomer solution, etc.) was preciselyweighed using a heat-resistant container, such as a metal cup, etc., andthe precisely-measured weight of the sample was defined as “A” g. Theheat-resistant container containing the sample was placed in an electricoven, and then heated and dried while raising the temperature gradually:120° C. for 12 minutes, 180° C. for 12 minutes, 260° C. for 30 minutes,and 300° C. for 30 minutes. The solid matter weight (nonvolatile matterweight) obtained was defined as “B” g. Five A values and five B valuesobtained from the same sample were measured (n=5), and applied to thefollowing formula (I) to determine nonvolatile matter content. Theaverage of the values obtained from the five samples was defined as thenonvolatile matter content in the invention.Nonvolatile matter content=B/A×100(%)  (I)

EXAMPLE C-2

22.8 g of methanol and 160 g of N-methyl-2-pyrrolidone were added to 35g (50 mol %) of a-BPDA and 35 g (50 mol %) of s-BPDA to react at a bathtemperature of 80° C. under a nitrogen stream. After cooling the bathtemperature to 65° C., 47.6 g of 4,4′-diaminodiphenyl ether (ODA) wasadded, followed by gentle stirring, giving 300.4 g of nylon salt monomersolution. This solution had a viscosity of 1.8 poise and a nonvolatilematter content of 36.3% by weight.

Separately, 47.6 g of ODA was added to 488 g of N-methyl-2-pyrolidoneunder a nitrogen stream. The mixture was kept warm at 50° C., andcompletely dissolved by stirring. 70 g of s-BPDA was gradually added tothis solution, giving 605.6 g of a polyamic acid solution. This polyamicacid solution had a number average molecular weight of 12000, viscosityof 12 poise, and nonvolatile matter content of 18.0% by weight.

100 g of the nylon salt monomer solution and 80 g of the polyamic acidsolution were mixed, giving 180 g of a polyimide-based precursorsolution having a viscosity of 5.2 poise and a nonvolatile mattercontent of 28.2% by weight. 7.5 g of acidic carbon black (pH 3.0) and16.7 g of N-methyl-2-pyrrolidone were added to 150 g of this precursorsolution to uniformly disperse the carbon black using a ball mill. Thismasterbatch solution had a nonvolatile matter content of 28.6% byweight; CB content in the nonvolatile matter of 15.1% by weight; meanparticle diameter of carbon black of 0.31 μm; and maximum particlediameter thereof of 0.77 μm. Ten days later, the mean particle diameterand maximum particle diameter of the carbon black hardly changed, andwere 0.31 μn and 0.88 μm, respectively.

EXAMPLE C-3

22.8 g of methanol and 250 g of N-methyl-2-pyrrolidone were added to 21g (30 mol %) of a-BPDA and 49 g (70 mol %) of s-BPDA to react at a bathtemperature of 80° C. under a nitrogen stream. After cooling the bathtemperature to 65° C., 47.6 g of 4,4′-diaminodiphenylether (ODA) wasadded, followed by gentle stirring, giving 390.4 g of nylon salt monomersolution. This solution had a viscosity of 0.7 poise and nonvolatilematter content of 27.9% by weight.

To 200 g of the nylon salt monomer solution was added 110 g of apolyamideimide solution (VYLOMAX HR-16NN, a product of TOYOBO) having anumber average molecular weight of 21000, solids content of 14% byweight, and viscosity of 500 poise), giving 310 g of polyimide-basedprecursor solution having a viscosity of 18 poise and a nonvolatilematter content of 23.0% by weight.

10.9 g of acidic carbon black (pH 3.0) and 25.2 g ofN-methyl-2-pyrrolidone were added to 260 g of this precursor solution touniformly disperse the carbon black using a ball mill. This masterbatchsolution had a nonvolatile matter content of 23.9% by weight; CB contentin the nonvolatile matter of 15.4% by weight; mean particle diameter ofcarbon black of 0.215 μm; and the maximum particle diameter of carbonblack of 0.51 μm. Ten days later, the mean particle diameter and maximumparticle diameter of the carbon black hardly changed, and were 0.218 μmand 0.58 μm, respectively.

REFERENCE EXAMPLE C-1

To 200 g of the nylon salt monomer solution as prepared in Example C-1were added 13.5 g of acidic carbon black (pH 3.0) and 120 g of organicsolvent (NMP). The mixture was primarily dispersed using a ball mill.This solution had a viscosity of 5 poise; nonvolatile matter content of25.8% by weight; CB content in the nonvolatile matter of 15.7% byweight; mean particle diameter of carbon black of 0.39 μm; and maximumparticle diameter of carbon black of 2.26 μm. Ten days later, the meanparticle diameter and maximum particle diameter of the carbon black were0.79 μm and 7.70 μm, respectively. It was confirmed that the carbonblack particles had aggregated.

REFERENCE EXAMPLE C-2

47.6 g of ODA was added to 450 g of N-methyl-2-pyrolidone under anitrogen stream. The mixture was kept warm at 50° C., and completelydissolved by stirring. 70 g of s-BPDA was gradually added to thissolution, giving 567.6 g of polyamic acid solution. This polyamic acidsolution had a number average molecular weight of 5000, viscosity of 6.6poise, and nonvolatile matter content of 19.2% by weight. 80 g of thissolution and 100 g of the nylon salt monomer solution as prepared inExample C-2 were mixed, giving 180 g of a polyimide-based precursorsolution. To this precursor solution were added 9.5 g of acidic carbonblack (pH 3.0) and 120 g of organic solvent (NMP). The mixture wasprimarily dispersed using a ball mill. This solution had a viscosity of6 poise; nonvolatile matter content of 19.8% by weight; CB content inthe nonvolatile matter of 15.5% by weight; mean particle diameter ofcarbon black of 0.26 μm; and maximum particle diameter of 0.87 μm. Tendays later, the mean particle diameter and maximum particle diameter ofthe carbon were 0.77 μm and 5.10 μm, respectively. It was confirmed thatthe carbon black particles had aggregated.

EXAMPLE C-4 Preparation of a Tubular Polyimide-Based Film by RotationalMolding

The solutions as prepared in Examples C-1, C-2, C-3, and ReferenceExamples C-1 and C-2 were uniformly applied, in a width of 480 mm, tothe inside of cylindrical metal molds with an outer diameter of 300 mm,inner diameter of 270 mm, and length of 500 mm while rotating the metalmold at rotational speed of 100 rpm (10.5 rad/s). The coating thicknesswas determined based on the nonvolatile matter content in such a manneras to obtain a polyimide belt thickness of 100 μm. The solvent wasevaporated by heating to 110° C. over 60 minutes, and further heatingwhile maintaining the temperature at 110° C. for 120 minutes. Thus, aself-supporting tubular article was obtained.

Subsequently, this tubular article was placed in a high temperatureheating furnace while adhered to the inside of the cylindrical metalmold. The temperature of the furnace was increased to 320° C. over 120minutes, at which the furnace was heated for 60 minutes forpolyimidization, giving a tubular polyimide film. After cooling to roomtemperature, the tubular polyimide film was removed from the metal mold.The surface condition was evaluated visually.

The surface resistivity (SR) and volume resistivity (VR) were measuredas follows. A sample 400 mm long was cut from the obtained tubularpolyimide film and was measured using a resistivity meter, “HirestaIP/HR probe” manufactured by Mitsubishi Chemical Corporation at 12points in total: three points in the width direction and four points inthe vertical direction (circumference) at the same pitch. The averagevalues were then obtained.

Note that the volume resistivity VR was measured while applying avoltage of 100 V, 10 seconds after beginning to apply the voltage and SRwas measured while applying a voltage of 500 V, 10 seconds afterbeginning to apply the voltage.

The measurement results are summarized in Table C-1. Table C-1 shows theaverage and standard deviations of surface resistivities and volumeresistivities in terms of log. Note that the CB content in the tubulararticle and the thickness thereof are also shown in Table C-1. TABLE C-1Ex. Ex. Ex. Ref. Ex. Ref. Ex. C-1 C-2 C-3 C-1 C-2 Surface condition FineFine Fine Aggregate Aggregate Front surface Average 10.28 10.51 10.347.01 8.84 Log (Ω/sq) Standard deviation 0.15 0.07 0.03 0.05 0.10 Rearsurface Average 10.31 10.53 10.37 8.83 10.28 Log (Ω/sq) Standarddeviation 0.14 0.07 0.03 0.61 0.14 Volume resistivity Average 8.63 8.638.92 9.64 8.7 Log (Ω · cm) Standard deviation 0.07 0.04 0.06 0.26 0.2Difference in surface Index 0.02 0.02 0.03 1.82 1.44 resistivitiesbetween front and rear surfaces Difference in surface Index 1.66 1.881.42 −2.62 0.14 resistivities between front and rear surfaces CB content15.1 15.1 15.4 15.7 15.5 (% by weight) Average thickness 100 100 100 100100 (μm)

Table C-1 shows that the standard deviations of the surfaceresistivities and the volume resistivities in the tubular articles ofExamples are very small, i.e., less variation, compared with those ofthe tubular articles of the Reference Examples.

Moreover, the differences in surface resistivities (in terms of log)between the front and rear surfaces of the tubular articles of Examplesare extremely small compared with those of the tubular articles of theReference Examples, and thus the tubular articles of Examples haveadvantageous properties as intermediate transfer belts for use inelectrographic systems.

Furthermore, in general, an increase in the heating temperatureelevation rate during film formation lowers the value (Log (SR/VR))obtained by subtracting the volume resistivity in terms of log (LogVR)from the surface resistivity in terms of log (LogSR). Therefore, the useof a film with such characteristics for a transfer belt results infailure of appropriate electrically charging and/or electricallydischarging, which leads to poor image quality. It was however foundthat this value is maintained as high as 1.0-2.0 by the use of asemi-conductive PI precursor composition of the invention.

In contrast, the front surface resistivities of the tubular articles ofthe Reference Examples were smaller than the rear surface resistivitiesthereof. A concentration gradient of carbon black presumably occurred inthe thickness direction of the tubular articles. As a result, the volumeresistivity was high and variation was large.

D. FOURTH EMBODIMENT

The fourth embodiment will be described in much greater detail withreference to Examples and Comparative Examples. Hereinafter,2,3,3′,4′-biphenyltetracarboxylic dianhydride is referred to as “a-BPDA”and 3,3′,4,4′-biphenyltetracarboxylic dianhydride is referred to as“s-BPDA”.

EXAMPLE D-1

To 153 g of N-methyl-2-pyrrolidone as an organic polar solvent, 27 g ofacidic carbon black (pH 3.0, volatile matter 14.5%) was added. Themixture was preliminarily dispersed, followed by primary dispersionusing a ball mill. The mean particle diameter of carbon black was 0.29μm and the maximum particle diameter thereof was 0.55 μm. Subsequently,to 120 g of this solution, 22.8 g of methanol, 14 g of a-BPDA and 56 gof s-BPDA were added to react at a bath temperature of 60° C. under anitrogen stream.

After cooling the bath temperature to 50° C., 47.6 g of4,4′-diaminodiphenyl ether (ODA) was added, followed by gentle stirring,giving 260 g of a carbon black-dispersed high-concentrationpolyimide-precursor composition comprising monomers. The solution had aviscosity of 32 poise; nonvolatile matter content of 48.9% by weight; CBcontent in the nonvolatile matter of 14.2% by weight; mean particlediameter of carbon black of 0.29 μm; and maximum particle diameterthereof of 0.58 μm. Ten days later, the mean particle diameter and themaximum particle diameter of the carbon black hardly changed, and were0.31 μm and 0.67 μm, respectively.

The “nonvolatile matter content” in the specification was calculated asfollows. A sample (carbon black-dispersed high-concentrationpolyimide-precursor composition) was precisely weighed using aheat-resistant container, such as a metal cup, etc., and theprecisely-measured weight of the sample was defined as “A” g. Theheat-resistant container containing the sample was placed in an electricoven, and then heated and dried while raising the temperature gradually:120° C. for 12 minutes, 180° C. for 12 minutes, 260° C. for 30 minutes,and 300° C. for 30 minutes. The solid matter weight (nonvolatile matterweight) obtained was defined as “B” g. Five A values and five B valuesobtained from the same sample were measured (n=5), and applied to thefollowing formula (I) to determine the nonvolatile matter content. Theaverage of the values obtained from the five samples was defined as thenonvolatile matter content in the invention.Nonvolatile matter content=B/A×100(%)  (I)

EXAMPLE D-2

To 120 g of N-methyl-2-pyrrolidone as an organic polar solvent, 10 g offurnace black (pH 9.0, volatile matter 1.5%) was added. The mixture waspreliminarily dispersed, followed by primary dispersion using a ballmill. The mean particle diameter of carbon black was 0.67 μm and themaximum particle diameter thereof was 3.92 μm. Subsequently, to 12.5 gof this solution, 35 g of a-BPDA, 35 g of s-BPDA, and 22.B g of methanolwere added to react at a bath temperature of 70° C. under a nitrogenstream. After cooling the bath temperature to 50° C., 47.6 g of4,4′-diaminodiphenyl ether (ODA) was added, followed by gentle stirring,giving 265 g of a carbon black-dispersed high-concentrationpolyimide-precursor composition comprising monomers. This solution had aviscosity of 12 poise; nonvolatile matter content of 44.7% by weight; CBcontent in the nonvolatile matter of 8.2% by weight; mean particlediameter of carbon black of 0.77 μm; and maximum particle diameter ofcarbon black of was 3.92 μm. Ten days later, the mean particle diameterand the maximum particle diameter of the carbon black hardly changed,and were 0.77 μm and 4.47 μm, respectively.

COMPARATIVE EXAMPLE D-1

To 600 g of high-molecular-weight polyamic acid solution prepared froms-BPDA and ODA (viscosity 50 poise, nonvolatile matter content 18.0% byweight), 20 g of acidic carbon black (pH 3.0, volatile matter 14.5%) wasadded, followed by primary dispersion using a ball mill. The resultanthad a high viscosity and was in a gel-like form. The solution was thenredispersed by adding 300 g of organic solvent (NMP). This solution hada viscosity of 8 poise; nonvolatile matter content of 13.9% by weight;CB content in the nonvolatile matter of 15.6% by weight; mean particlediameter of carbon black of 0.32 μm; and maximum particle diameterthereof of 0.77 μm. Ten days later, the mean particle diameter andmaximum particle diameter of the carbon black hardly changed, and were0.32 μm and 0.77 μm, respectively.

REFERENCE EXAMPLE D-1

To 35 g (50 mol %) of a-BPDA and 35 g (50 mol %) of s-BPDA, 22.8 g ofmethanol and 160 g of N-methyl-2-pyrrolidone were added to react under anitrogen stream at a bath temperature of 70° C. After cooling the bathtemperature to 60° C., 47.6 g of 4,4′-diaminodiphenyl ether (ODA) wasadded, followed by gentle stirring, giving 300.4 g of nylon salt monomersolution. This solution had a viscosity of 1.8 poise and a nonvolatilematter content of 36.3% by weight. To this solution, 16.5 g of acidiccarbon black (pH 3.0, volatile matter 14.5%) and 140 g of organic polarsolvent (NMP) were added, followed by primary dispersion using a ballmill. This solution had a viscosity of 5 poise; nonvolatile mattercontent of 27.5% by weight; CB content in the nonvolatile matter of12.3% by weight; mean particle diameter of carbon black of 0.47 μm; andmaximum particle diameter of carbon black of 1.73 μm. Ten days later,the mean particle diameter and maximum particle diameter of the carbonblack were 0.78 μm and 5.12 μm, respectively. It was confirmed that thecarbon black particles had aggregated.

EXAMPLE D-3 Preparation of a Tubular Polyimide Film by RotationalMolding

The solutions as prepared in Examples D-1 and D-2, Comparative ExampleD-1, and Reference Example D-1 were uniformly applied, in a width of 480mm, to the inside of cylindrical metal molds with an outer diameter of300 mm, inner diameter of 270 mm and length of 500 mm while rotating themetal mold at rotational speed of 100 rpm (10.5 rad/s). The coatingthickness was determined based on the nonvolatile matter content in sucha manner as to obtain a polyimide belt thickness of 100 μm. The solutionwas heated to 100° C. over 60 minutes to evaporate the solvent.Thereafter, evaporation of the solvent at 100° C. was visually observed,and the time required to complete solvent evaporation was measured.

Subsequently, the tubular article was placed in a high temperatureheating furnace while adhered to the inside of the cylindrical metalmold. The temperature of the furnace was increased to 320° C. over 120minutes, at which the furnace was heated for 60 minutes forpolyimidization. After cooling to room temperature, the tubularpolyimide film was removed from the metal mold. The measurement resultsare summarized in Table D-1. Note that the CB content in the tubulararticle and the thickness thereof are also shown in Table D-1.

The surface resistivity (SR) was measured as follows. A sample 400 mmlong was cut from the obtained tubular polyimide film and was measuredusing a resistivity meter, “Hiresta IP-HR probe” manufactured byMitsubishi Chemical Corporation at 12 points in total: three points inthe width direction and four points in the vertical direction(circumference) at the same pitch. The averages of all the measuredvalues are shown. The surface resistivity (SR) was measured whileapplying a voltage of 500 V, 10 seconds after beginning to apply thevoltage. TABLE D-1 Time required for evaporation of CB content In theThickness of the Film-formation solvent Surface resistivity tubulararticle tubular article solution (minutes) Surface condition (Ω/sq) (%by weight) (μm) Ex. D-1 45 Fine 2.5 × 10¹⁰ 14.2 94-102 Ex. D-2 60 Fine5.0 × 10⁷ 8.1 96-103 Com. Ex. D-1 170 Fine 2.0 × 10¹⁰ 15.6 88-102 Ref.Ex. D-1 110 Aggregation of 2.0 × 10⁶ 12.3 95-104 carbon black

According to the prior-art method (Comparative Example), the productionefficiency is extremely low because the nonvolatile matter content inthe film-formation starting material is low and considerable time isneeded to evaporate the large amount of organic polar solvent. Moreover,in a film-formation method comprising a step of adding and dispersing CBin a monomer solution, etc., the reaction of the monomer solutionproceeds due to heat produced by dispersion, which makes the solutioncondition unstable.

EFFECTS OF THE INVENTION

The present invention can form a high-quality nonconductive orsemi-conductive seamless (jointless) tubular polyimide film in a simple,efficient, and economical manner.

More specifically, according to the first embodiment, a seamless tubularPI film can be directly obtained from a polyimide monomer startingmaterial having a specific composition with a rotationally moldingmember. Moreover, considerable time can be saved compared with prior-artmethods for producing seamless tubular PI films via polyamic acids. Inaddition, the productivity is improved by significantly rationalizingproduction control and a more stable and higher-quality tubular PI filmcan also be obtained. The seamless tubular PI film obtained can be usedfor various applications, and in particular, a semi-conductive seamlesstubular film can be used more advantageously as an intermediate transferbelt in an electrophotographic system for use in a color printer, colorcopier, etc.

The semi-conductive tubular PI film of the second embodiment hashomogeneous electrical resistivity because it is formed using, as a filmformation starting material, an aromatic amic acid oligomer obtained bypolycondensation of a specific aromatic tetracarboxylic acid componentand a specific aromatic diamine component. More specifically, thesemi-conductive tubular PI film of the invention has excellentproperties, such as less variation in surface and volume resistivitiesand small difference in surface resistivities (in terms of logarithm)between the front and rear surfaces. Moreover, the value obtained bysubtracting volume resistivity in terms of log (LogVR) from surfaceresistivity in terms of log (LogSR) can be maintained as high as1.0-3.0. Therefore, the semi-conductive tubular PI film of the inventioncan be advantageously used as an intermediate transfer belt for use in acolor copier, etc., and electrically charging and/or electricallydischarging can be appropriately performed, thereby achieving excellentimage processing.

Since the semi-conductive tubular PI film of the third embodiment hasuniform electrical resistivity because it is formed using, as afilm-formation starting material, a semi-conductive polyimide-basedprecursor composition obtained by uniformly dispersing carbon black in amixed solution comprising a nylon salt monomer solution and ahigh-molecular-weight polyimide precursor solution orhigh-molecular-weight polyamideimide solution. Therefore, thesemi-conductive tubular PI film of the invention has excellentproperties, such as less variation in surface and volume resistivitiesand small difference in surface resistivities (in terms of logarithm)between the front and rear surfaces. Therefore, the semi-conductivetubular PI film of the invention can be suitably used as an intermediatetransfer belt for use in a color copier, etc., and electrically chargingand/or electrically discharging can be appropriately performed, therebyachieving excellent image processing.

In the semi-conductive high-concentration PI precursor composition ofthe fourth embodiment, CB powder is uniformly dispersed and the storagestability of the uniform dispersion of CB powder is remarkably improved.An electrically conductive tubular PI film prepared by rotationallymolding the semi-conductive PI precursor composition has an excellentelectrical conductivity; extreme stability and uniform electricalresistivity in the thickness direction. More specifically, by the use ofsuch film for an intermediate transfer belt in an electrophotographicsystem for use in a color printer, color copier, etc., electricallycharging and/or electrically discharging can be appropriately performed,thereby achieving excellent image processing. The semi-conductivehigh-concentration PI precursor composition of the invention is preparedby dissolving the film-formation starting material monomers in thecarbon black dispersion, thereby dramatically increasing the nonvolatilematter content to about 35 to about 60% by weight. Therefore, thesemi-conductive high-concentration PI precursor composition of theinvention can readily form a thick film. Moreover, the invention canreduce the amount of solvent required for film formation, therebylowering solvent cost and facilitating evaporation to remove a solvent.

1. A seamless tubular polyimide film, comprising polyimide having atleast two aromatic tetracarboxylic acid components having a mixture of15 to 55 mol % of asymmetric aromatic tetracarboxylic acid component and85 to 45 mol % of symmetric aromatic tetracarboxylic acid component andat least one aromatic diamine component, the seamless tubular polyimidefilm having a yield stress (σ_(Y)) of at least 120 MPa and having atensile strength to yield stress stress ratio (σ_(cr)/σ_(Y)) of at least1.10.
 2. A semi-conductive seamless tubular polyimide film, whereincarbon black is dispersed in polyimide having at least two aromatictetracarboxylic acid components having a mixture of 15 to 55 mol % ofasymmetric aromatic tetracarboxylic acid component and 85 to 45 mol % ofsymmetric aromatic tetracarboxylic acid component and at least onearomatic diamine component, the semi-conductive seamless tubularpolyimide film having a surface resistivity of 10³ to 10¹⁵ Ω/sq.
 3. Asemi-conductive seamless tubular polyimide film according to claim 2,wherein a log standard deviation of surface resistivity is 0.2 orsmaller, a log standard deviation of volume resistivity is 0.2 orsmaller, and a difference between a log surface resistivity and a logvolume resistivity is 0.4 or smaller.
 4. A method for producing aseamless tubular polyimide film, comprising: rotationally molding amixed solution substantially in a monomeric state having a mixture of anaromatic tetracarboxylic acid component comprising 15 to 55 mol % ofasymmetric aromatic tetracarboxylic acid and/or ester thereof and 85 to45 mol % of symmetric aromatic tetracarboxylic acid and/or ester thereofand an approximately equimolar amount of an aromatic diamine component,to form a tubular shape, and imidizing the tubular material by heating.5. A method for producing a semi-conductive seamless tubular polyimidefilm, comprising: mixing an aromatic tetracarboxylic acid componentcomprising 15 to 55 mol % of asymmetric aromatic tetracarboxylic acidand/or ester thereof and 85 to 45 mol % of symmetric aromatictetracarboxylic acid and/or ester thereof and an approximately equimolaramount of an aromatic diamine component, to form mixed solutionsubstantially in a monomeric state, dispersing 1 to 35 parts by weightof carbon black in the mixed solution, per 100 parts by weight of atotal amount of the aromatic tetracarboxylic acid component and thearomatic diamine component, to form a semi-conductive monomer mixedsolution, rotationally molding the semi-conductive monomer mixedsolution to form a tubular shape; and imidizing the tubular material byheating.
 6. A semi-conductive seamless tubular polyimide film for use inan intermediate transfer belt in an electrophotographic system producedby a production method of claim
 5. 7. A semi-conductive aromatic amicacid composition comprising: an aromatic amic acid oligomer obtained bypolycondensation of at least two aromatic tetracarboxylic acidderivatives and an approximately equimolar amount of at least onearomatic diamine; carbon black; and an organic polar solvent.
 8. Asemi-conductive aromatic amic acid composition according to claim 7,wherein the aromatic amic acid oligomer is obtained by polycondensationof at least two aromatic tetracarboxylic dianhydrides and anapproximately equimolar amount of said at least one aromatic diamine inan organic polar solvent at about 8° C. or lower.
 9. A semi-conductivearomatic amic acid composition according to claim 8, wherein said atleast two aromatic tetracarboxylic dianhydrides are 15 to 55 mol % ofasymmetric aromatic tetracarboxylic dianhydride and 85 to 45 mol % ofsymmetric aromatic tetracarboxylic dianhydride.
 10. A semi-conductivearomatic amic acid composition according to claim 7, wherein thearomatic amic acid oligomer is obtained by polycondensation of at leasttwo aromatic tetracarboxylic acid diesters and an approximatelyequimolar amount of said at least one aromatic diamine in an organicpolar solvent at about 90 to about 120° C.
 11. A semi-conductivearomatic amic acid composition according to claim 10, wherein said atleast two aromatic tetracarboxylic acid diesters are 15 to 55 mol % ofasymmetric aromatic tetracarboxylic acid diester and 85 to 45 mol % ofsymmetric aromatic tetracarboxylic acid diester.
 12. A semi-conductivearomatic amic acid composition according to claim 7, wherein a numberaverage molecular weight of the aromatic amic acid oligomer is about1000 to about
 7000. 13. A semi-conductive aromatic amic acid compositionaccording to claim 7, wherein carbon black is present in an mount ofabout 3 to about 30 parts by weight per 100 parts y weight of a totalamount of aromatic tetracarboxylic acid component and organic diamine.14. A method for producing a semi-conductive seamless tubular polyimidefilm, comprising: rotationally molding a semi-conductive aromatic amicacid composition according to claim 7; followed by heating.
 15. Asemi-conductive seamless tubular polyimide film for use in anintermediate transfer belt in an electrophotographic system produced bya production method according to claim
 14. 16. A method for producing asemi-conductive aromatic amic acid composition comprising: subjecting atleast two aromatic tetracarboxylic acid derivatives and an approximatelyequimolar amount of at least one aromatic diamine to partialcondensation polymerization in an organic polar solvent, therebyyielding an aromatic amic acid oligomer solution; and uniformly mixingelectrically conductive carbon black powder with the oligomer solution.17. A semi-conductive polyimide-based precursor composition, whereincarbon black is uniformly dispersed in a mixed solution prepared bymixing a high-molecular-weight polyimide precursor solution orhigh-molecular-weight polyamideimide solution in a nylon salt monomersolution in which at least two aromatic tetracarboxylic acid diestersand an approximately equimolar amount of at least one aromatic diamineare dissolved in an organic polar solvent.
 18. A semi-conductivepolyimide-based precursor composition according to claim 17, whereinsaid at least two aromatic tetracarboxylic acid diesters are 10 to 55mol % of asymmetric aromatic tetracarboxylic acid diester and 90 to 45mol % of symmetric aromatic tetracarboxylic acid diester.
 19. Asemi-conductive polyimide-based precursor composition according to claim17, wherein said at least two aromatic tetracarboxylic acid diesters are10 to 55 mol % of asymmetric 2,3,3′,4′-biphenyl tetracarboxylic aciddiester and 90 to 45 mol % of symmetric 3,3′,4,4′-biphenyltetracarboxylic acid diester.
 20. A semi-conductive polyimide-basedprecursor composition according to claim 17, wherein thehigh-molecular-weight polyimide precursor solution is a polyamic acidsolution whose number average molecular weight is 10000 or larger andthe high-molecular-weight polyamideimide solution is a polyamideimidesolution whose number average molecular weight is 10000 or larger.
 21. Asemi-conductive polyimide-based precursor composition according to claim20, wherein the polyamic acid solution whose number average molecularweight is 10000 or larger is produced by reaction of diaminodiphenylether and an approximately equimolar amount of biphenyltetracarboxylicdianhydride in an organic polar solvent.
 22. A semi-conductivepolyimide-based precursor composition according to claim 20, wherein thepolyamideimide solution whose number average molecular weight is 10000or larger is produced by reaction of acid anhydride comprisingtrimellitic acid anhydride and benzophenone tetracarboxylic dianhydrideand an approximately equimolar amount of aromatic isocyanate in anorganic polar solvent.
 23. A method for producing a semi-conductiveseamless tubular polyimide film, comprising: rotationally molding asemi-conductive polyimide-based precursor composition according to claim17, to form a tubular shape; and imidizing the tubular material byheating.
 24. A semi-conductive seamless tubular polyimide-based film foruse in an intermediate transfer belt in an electrophotographic systemproduced by a production method according to claim 23, whose surfaceresistivity is 10⁷ to 10¹⁴Ω/sq.
 25. A method for producing asemi-conductive polyimide-based precursor composition, comprising:mixing a high-molecular-weight polyimide precursor solution orhigh-molecular-weight polyamideimide solution in a nylon salt monomersolution in which at least two aromatic tetracarboxylic acid diestersand an approximately equimolar amount of at least one aromatic diamineare dissolved in an organic polar solvent to prepare a mixed solution,and uniformly dispersing carbon black in the mixed solution.
 26. Amethod for producing a high-concentration semi-conductive polyimideprecursor composition, comprising: uniformly dispersing carbon black inan organic polar solvent to give a carbon black dispersion anddissolving aromatic tetracarboxylic acid diester and an approximatelyequimolar amount of aromatic diamine in the carbon black dispersion. 27.A method for producing a high-concentration semi-conductive polyimideprecursor composition according to claim 26, wherein the aromatictetracarboxylic acid diester is a mixture of 10 to 55 mol % ofasymmetric aromatic tetracarboxylic acid diester and 90 to 45 mol % ofsymmetric aromatic tetracarboxylic acid diester.
 28. A method forproducing a high-concentration semi-conductive polyimide precursorcomposition according to claim 26, wherein the aromatic tetracarboxylicacid diester is a mixture of 10 to 55 mol % of asymmetric2,3,3′,4′-biphenyl tetracarboxylic acid diester and 90 to 45 mol % ofsymmetric 3,3′,4,4′-biphenyl tetracarboxylic acid diester.
 29. A methodfor producing a high-concentration semi-conductive polyimide precursorcomposition according to claim 26, wherein carbon black is present in anamount of 5 to 35 parts by weight per 100 parts by weight of a totalamount of the aromatic tetracarboxylic acid and the aromatic diamine.30. A high-concentration semi-conductive polyimide precursor compositionproduced by a production method of claim
 26. 31. A method for producinga semi-conductive seamless tubular polyimide film, comprising:rotationally molding a high-concentration semi-conductive polyimideprecursor composition according to claim 30, to form a tubular shape;and imidizing the tubular material by heating.
 32. A semi-conductiveseamless tubular polyimide film for use in an intermediate transfer beltin an electrophotographic system produced by a method according to claim31, whose surface resistivity is 10⁷ to 10¹⁴ Ω/sq.